LECTURE NOTE
PELUMASAN DAN
TEKNOLOGI PELUMAS
(Dosen Sukirno)
1
INTRODUCTION
TRIBOLOGY, FRICTION, WEAR, LUBRICATION
2
LUBRICANT & LUBRICATION
LIQUID, SOLID,GAS LUBRICANT
LUBRICATION REZIMES
NECESSARRY PROPERTIES OF LIQUID LUBRICANT
THE ROLE OF ADDITIVES
3
BASE OIL & ADITIVE TECHNOLOGY
MINERAL OIL
SYNTHETIC FLUIDS
BIO LUBRICANT
4
LUBRICANT FORMULATION
ENGINE OILS
INDUSTRIAL LUBRICANTS
GREASE
5
LUBRICANT DEGRADATION
OXIDATIVE DEGRADATION
DEPARTEMEN TEKNIK KIMIA
FT-UI
1. INTRODUCTION
Tribologi, Friksi, Keausan Dan Pelumasan
1.1 Tribologi
Tribology berasal dari kata tribos (bahasa Yunani yang berarti rubbing, dan logy
atau logia artinya studi. Tribologi adalah studi tentang interaksi atau rubbing dari
permukaan yang saling bergerak relatif..
Walaupun penggunaan pelumas sudah dimulai sejak jaman kuno, misalnya pada
peralatan seperti roda pembuatan keramik, engsel pintu, roda kereta, seluncur untuk
menyeret batu besar/patung di Mesir dll. Namun pembahasan secara ilmiah terhadap
teknologi pelumas dan pelumasan ini relatif baru. Perumusan pertama hukum tribologi
baru mengemuka pada abad 15, pada saat itu insinyur-artis, Leonardo da Vinci (1452-
1519), menemukan bahwa gaya friksi sebanding dengan gaya normal. Terminologi
TRIBOLOGI diperkenalkan baru sekitar tahun 1966 sebagai ilmu sain tentang friksi
(friction), keausan (wear) pelumasan (lubrication), dan sudah digunakan secara global
untuk menggambarkan aktifitas yang jangkauannya luas ini.
Friction biasanya merupakan cabang ilmu dari bidang teknik mesin ataupun fisika.
Wear biasanya bagian dari ilmu bahan atau metalurgi. Lubrication adalah cabang Dengan
demikian tribologi adalah ilmu indisipliner dalam semua aspek, dan memberikan dasar sain
untuk memahami fenomena gesekan dan pelumasan dalam sistim tribologi. Efisiensi
pelumasan dan aplikasi pelumas selanjutnya tergantung pada paremeter kunci seperti
konsistensi, properti aliran atau viskositas untuk cairan yang selalui muncul pada
spesifikasi semua pelumas.
1.2 Friksi (Friction)
Friksi adalah gaya yang menahan gerakan sliding atau rolling satu benda terhadap
benda lainnya. Friksi merupakan faktor yang penting dalam mekanisme operasi sebagian
besar peralatan atau mesin.
Friksi besar (high friction) dibutuhkan untuk bekerjanya mur dan baut, klip kertas,
penjepit (tang catut), sol sepatu, alat pemegang dll. Gaya friksi dibutuhkan pada saat kita
jalan agar tidak terpeleset. Friksi juga dibutuhkaan agar dapat menumpuk pasir, apel dll.
Namun friksi juga merupakan tahanan tehadap gerakan yang bersifat merugikan.20%
tenaga mesin mobil dipergunakan untuk mengatasi gaya friksi pada elemen mesin yang
bergerak.
Oleh karena itu friksi kecil (low friction), dikehendaki untuk benda yang bergerak seperti
mesin tenaga (engine), ski, elemen arloji/jam dll.
Disamping itu juga dibutuhkan friksi konstan (constant friction ) yaitu untuk rem, dan
kopling agar geakkan tidak tersendat sendat.
Friksi telah dipelajari sebagai cabang mekanika beberapa ratus tahun yang lalu, dan hukum
dan metode untuk memperkirakan besarnya friksi telah diketahui 2 abad lalu. Manun
mekanisme friksi, yaitu proses hilangnya energi jika dua permukaan saling bergesek tidak
dapat diterangkan dengan baik.
Penyebab utama friksi antara dua logam kelihatannya adalah gaya tarik (adesi) daerah
kontak (contact region) dari permukaan yang secara mokroskopik tidak beraturan. Jika
diperbesar permukaan menyerupai bukit dan lembah.
Jika ada beban, ketika 2 permukaan bersinggungan, dua bukit menempel (adesi atau
menyatu) atau terkunci dilembah permukaan dihadapannya. Friksi timbul akibat adanya
geseran (shearing) bukit yang menyatu tersebut dan jua akibat ketidak teraturan
permukaan.tersebut, bagian yang keras tertanam kepada bagian lunak.
Friksi dari slidding dua benda padat yang diperoleh dari ekperimen sederhana
menghasilkan kesimpulan sbb :
1. Besarnya friksi hampir tidak bergantung pada luas kontak .
Jika sebuah bata ditarik diatas meja, gaya friksi tetap sama, baik posisi bata
berdidri ataupun tidur. (Leonardo da Vinci (1452-1519)
2. Friksi berbanding lurus dengan beban yang bekerja pada permukaan.
Jika bata ditumpuk empat ditarik diatas meja, besarnya friksi empatkalinya friksi
satu batayang ditarik..
Jadi rasio gaya friksi F terhadap beban L adalah tetap.
Rasio yang tetap tersebut disebut koefisen friksi (coefficient of friction ) dan biasanya
diberi simbol huruf Yunani mu (μ ). Secara matematik persamaan dapat ditulis sbb :
L
F
μ =
Koefisien friksi tidak punya satuan, karena friksi dan beban yang diukur dalam satuan gaya
(pound atau Newton) saling meniadakan.
Sebagai contoh : Harga koefisien friksi μ=0,5 untuk kasus bata ditarik diatas kayu yang
berarti bahwa dibtuhkan gaya sebesar setengah dari berat bata untuk mengatasi friksi, dan
menjaga bata bergerak secara konstan. Gaya friksi arahkan berlawanan dengan arah gerak
bata. Karena friksi timbul antara permukaan yang bergerak maka ini disebut friksi kinetik
(kinetic friction).
Ini untuk membedakan dengan friksi statik (static friction), yang bekerja pada permukaan
yang diam. Harga friksi statik selalu lebih besar dari friksi kinetik
Friksi rolling (rolling friction) terjadi jika suatu roda, slinder ataupun bola
menggelinding bebas diatas permukaan, sepertihalnya pada ball tau roller bearing. Sumber
friksi utama dalam gerakan rolling adalah disipasi energi yang meilbatkan deformasi
benda. Jika bola keras menggelinding diatas permukaan, bola sedikit peyang dan
permukaan sedikit legok pada daerah kontak. Deformasi elastik atau kompresi pada
daerah kontak tersebut merupakan penghambat gerakan dan energinya tidak kembali saat
benda kembali ke bentuk semula. Enegi yang hilang pada kedua bagian permukaan sama
dengan energi yang hilang pada bola yang jatuh dan terpantul. Besarny friksi slidding
pada umumnya 100 sampai 1000 kali lebih besar dibandingkan dengan friksi
rolling.Keuntungan gerakan rolling dipahami oleh manusia pendahulu sehingga ditemukan
roda.
1.3. Keausan (wear)
Keausan (wear) adalah hilangnya materi dari permukaan benda padat sebagai
akibat dari gerakan mekanik. Keausan umumnya sebagi kehilangan materi yang timbul
sebagai akibat interaksi mekanik dua permukaan yang bergerak slidding dan dibebani. Ini
merupakan fenomena normal yang terjadi jika dua permukaan saling bergesekan, maka
akan ada keausan.atau perpindahan materi
Contohnya uang logam manjadi tumpul setelah lama dipakai akibat bergesekan dengan
kain dan jari manusia. Pensil mejadi tumpul akibat bersesek dengan kertas, jalan kerena
menjadi legok atau tumpul akibat digelindingi oleh roda kereta terus menerus..
Hanya makhluk hidup (sendi tulang) yang tidak rusak akibat keausan disebabkan memilki
kemampuan penyembuhan diri. Dengan pertumbuhan. Namun ada juga organ yang tidak
punya kemampuan pulih, misalnya gigi. Studi tentang keausan secatra sistematik dihampat
oleh dua faktor utama yaitu;
1. Adanya sejumlah mekanisme proses keausan yang bekerja terpisah.
2. Kesulitan mengukur jumlah kecil materi yang terlibat.
Kesulitan ini dapat diatas menggunakan teknik penelusuran (tracer techniques) isotop
radioaktif yang memnungkinakn pengukuran jumlah kecil.
Dikenal ada jenis keausan 4 jenis keausan yaitu sebagai berikut :
Adhesive wear adalah jenis yang paling umum, timbul apabila terdapat gaya adesi kuat
diantara dua materi padat. Apabila dua permukaan ditekan bersama maka akan terjadi
kontak pada bagian yang menonjol. Apabila digeser maka akan terjadi penyambungan dan
jika geseran dilanjutkan akan patah. Dan jika patahan tidak terjadi pada saat
penyambungan maka yang timbul adalah keausan. Keausan adesi tidak diinginkan karena
dua alasan :
1. Kehilangan materi pada akhirnya membawa pada menurunnyanya unjuk kerja
suatu mekanisme.
2. Pembentukan partikel keausan pada pasangan permukaan slidding yang sangat
rapat dapat menyebabkan mekanisme terhambat atau mahkan macet, padahal umur
peralatan masih baru.
Keausan adesi beberapa kali lebih besar pada kondisi tanpa pelumasan dibandingkan
kondisi permukaan yang dipplumasi dengan baik.
Keausan abrasi (abrasive wear) terjadi apabila permukaan yang keras bergesekan dengan
permukaan yang lebih lunak., meninggalkan goresan torehan pada permukaan lunak.
Abrasi juga bisa disebabkan oleh patahan partikel keras yang bergeser diantara dua
permukaan lunak. Fragmen abrasif yang ada dalam fluida mengalir cepat juga dapat
menyebabkan tertorehnya permukaan, jika membentur permukaan pada kecepatan tingiii.
Karena keausan abrasi terjadii oleh adanya partikel lebih keras dari permukaan masuk
sistem, maka pencegahannya adalah dengan mengeliminasi komtaminan keras.
Corrosive wear occurs whenever a gas or liquid chemically attacks a surface left exposed
by the sliding process. Normally, when a surface corrodes, the products of corrosion (such
as patina) tend to stay on the surface, thus slowing down further corrosion. But, if
continuous sliding takes place, the sliding action removes the surface deposits that would
otherwise protect against further corrosion, which thus takes place more rapidly. A surface
that has experienced corrosive wear generally has a matte, relatively smooth appearance.
Surface-fatigue wear is produced by repeated high stress attendant on a rolling motion,
such as that of metal wheels on tracks or a ball bearing rolling in a machine. The stress
causes subsurface cracks to form in either the moving or the stationary component. As
these cracks grow, large particles separate from the surface and pitting ensues. Surfacefatigue
wear is the most common form of wear affecting rolling elements such as bearings
or gears. For sliding surfaces, adhesive wear usually proceeds sufficiently rapidly that there
is no time for surface-fatigue wear to occur.
Though the wear process is generally thought of as harmful, and in most practical
situations is so, it has some practical uses as well. For example, many methods of
producing a surface on a manufactured object depend on abrasive wear, among them filing,
sanding, lapping, and polishing.
Many writing instruments, principally the pencil, crayon, and chalk, depend for their effect
on adhesive wear. Another use is seen in the wear of the incisor teeth of rodents. These
teeth have hard enamel covering along the outer curved surface but only soft dentine on the
inner surface.
Hence, abrasive and adhesive wear, which occurs more rapidly on the softer side, acts to
maintain a sharp cutting edge on the teeth.
1.4 Pelumasan (Lubrication)
Pelumasan adalah tindakan menempatkan pelumas antara permukaan yang saling
bergeser untuk mengurangi keausan dan friksi. Pengembangan dan uji pelumas merupakan
aspek tribologi yang menerima perhatian sangat besar. Satu perusahaan pelumas bisa
memasarkan ratusan jenis pelumas dan tidak ada.
Penggunakan pelumas pada jaman kuno, seperti tergambar pada relief dinding batu
di Mesir 4,000 yl., yaitu orang melumasi jalan saat menyeret patung batu yang berat.
Pelumasan pada jaman modern, sistim pelumasan didesain untuk mengurangi keausan alat
sehingg dapat beroperasi lama dan tanpa pemeliharaan.
Alam menggunakan cairan yang disenbut synovial fluid pada pelumasan tulang
sendi hewan dan manusia. Sedangkan manusia jaman prasejarah menggunakan lumpur
untuk menarik seluncur.
Pelumas dari lemak binatang dipakai untuk gerobak pertama, dan terus digunakan
sampai abad 19 ketika industri minyak bumi (petroleum) muncul, yang kemudian mejadi
sumber utama pelumas mineral (mineral oil) atau pelumas petro (petroleum lubricant).
Kemampuan pelumas petro terus dikembangkan untuk memenuhi bervariasi kebutuhan
spesifik seperti sepeda motor, mobil, pesawat, mesin turbo, kereta api, mesin pembangkit
tenaga dll. dan tuntutan bertambahnya kecepatan dan kapasitas mesin transportasi maupun
mesin industri.
Zaman jet dan ruang angkasa memperbaharui minat orang pada pelumas sintetik
(synthetic lubricants) karena menawarkan unjuk kerja superior dibandingkan pelumas
petro. Minyak lumas sintetik walaupun sudah banyak dipasarkan namun harganya masih
beberapa kali lebih mahal dibandingkan dengan pelumas petro konvensional.
Akhir-akhir ini kepedulian orang terhadap lingkungan memperbarui minat pada
pelumas bio dari minyak nabati (vegetable oils) yang bersifat ramah lingkungan.
Jenis pelumasan
Ada tiga jenis pelumasan yaitu pelumasan oleh lapisan cairan (Fluid-film),
pelumasan Batas ( Boundary Lubrication), Pelumasan padat ( Solid Lubrication)
1. Pelumasan Lapisan Fluida (Fluid-film lubrication)
Pelumasan ini dilakukan dengan menyisipkan (interposing) lapisan cairan yang
dapat memisahkan secara sempurna permukaan yang bergerak. Lapisan cairan mungkin
secara sengaja disediakan seperti minyak lumas pada bantalan (bearings) atau tanpa
sengaja misalnya air yang tergenang di jalan dan roda mobil.
Meskipun umumnya fluida berupa cairan, tetapi dapat juga dari gas. Gas yang digunakan
umumnya adalah udara. Untuk menjaga agar permukaan tetap terpisahkan maka perlu
adanya kesetimbangan antara gaya tekanan oleh lapisan fluida dan gaya beban pada
permukaan yang bergesek.
Jika tekanan antara dua permukaan ditimbulkan oleh hasil gerakan dan bentuk daari
permukaan tersebut, sistim ini disebut pelumasan hidrodinamik (hydrodynamic
lubrication). Jenis pelumasan ini bergantung pada viskositas dari pelumas cair.
Jika tekanan fluida diantara dua permukaan diberikan dari luar, misalnya pompa, pelumsan
ini disebut pelumasan hidrostatik (hydrostatic lubrication).
2. Pelumasan Batas (Boundary lubrication)
Suatu kondisi antara pelumasan lapisan fluida dan keadaan tanpa pelumas dan ada
disebut pelumasan batas (boundary lubrication). Pada kondisi ini properti permukaan dan
properti pelumas menentukan besarnya friksi sistim ini.
Pelumasan batas menunjukkan salah satu fenomena pelumasan yang sangat penting, yang
dijumpai terutama pada saat mesin start dari keadaan berhenti.
3. Pelumasan Padat (Solid lubrication)
Materi padat seperti graphite, molybdenum disulfide (Moly) dan PTFE (Teflon)
digunakan secara luas jika pelumas biasa tidak memiliki kemampuan menahan beban dan
suhu yang ektrim. Pelumas tidak hanya dari lemak, serbuk, gas tapi juga kadang bahan
logam dipakai sebagai permukaan gesek pada beberapa mesin.
Beberapa puluh tahun terakhiri ini juga dikenal jenis pelumas baru yang disebut
pelumas sol (sol-lube). Pelumas ini merupakan koloid, yaitu suspensi pelumas padat dalam
pelumas cair.
1.6 Apa yang ditawarkan oleh Tribologi ?
Fenomena yang menjadi perhatian tribology sangat fundamental dan sering ditemui
dalam kehidupan manusia, dalam lingkungan benda padat. Aplikasi tribologi yang telah
memberikan kemudahan bagi kehidupan kuno, juga diperlukan bagi kehidupan modern,
seperti yang terdapat pada banyak sistim mekanik yang bekerja berdasarkan nilai friction,
lubrication and wear. Dilain pihak dapat dijumpai efek tribologi yang menciptakan
kebisingan, sehingga diperlukan kehati hatian dalam mendesain sistim, agar tidak
menciptakan ketidak nyamanan akibat masalah friksi ataupun keausan berlebihan.
Secara umum dapat dikatakan bahwa friksi biasanya membuang energi yang cukup
besar, sedangkan keausan adalah membuang waktu produksi, karena harus mengganti
komponen mesin. Oleh karena itu tribologi mendapatkan perhation yang semakin
meningkat karena disadari bahwa energi yang terbuang akibat friksi dan wear sangat besar
(di USA lebih dari 6% Gross National Product [GNP]). Oleh karena itu potensi yang
dijanjikan dengan memperbaiki pengetahuan tribologi juga akan besar.
Seiring dengan perkembangan peralatan modern yang sangat komplek, kecepatan
dan panas tinggi, tribologi menawarkan suatu metode mengendalikan keausan berdasarkan
pendekatan sistematis dengan mengintegrasikan berbagai disiplin ilmu pengetahuan seperti
mekanika fluida, metalurgi, fisika-kimia permukaan dan pelumas.
Tujuan Penerapan Tribologi
• Meningkatkan pengertian apa yang terjadi diantara dua permukaan yang saling
bergesek.
• Mengoptimalkan unjuk kerja peralatan
• Mengurangi keausan dan konsumsi energi
Strategi Penyelesaian Berdasarkan :
• Pengetahuan yang mendalam tentang mekanisme dasar pelumasan,.
• Pengembangan pelumas yang dapat memberi unjuk kerja baik pada kondisi
temperatur, tekanan, dan lingkungan tertentu.
• Penyempurnaan desain dan geometri componen mesin yang mengurangi
gesekan dan keausan serta jumlah pelumas yang disuplai.
• Pemilihan bahan yang lebih tahan.
Penerapan pengetahuan tribologi menjajikan penghematan sebagai berikut
• Manpower savings
• Lubricant savings
• Invesment saving
• Less frictional dissipation
• Longer life of machines
• Fewer breakdown
• Less mantenance and replacement
2. LUBRICANT
2.1 Jenis Pelumas
A wide variety of lubricants are available. The principal types are reviewed here.
Liquid, oily lubricants
Animal and vegetable products were certainly man's first lubricants and were used in
large quantities. But, because they lack chemical inertness and because lubrication
requirements have become more demanding, they have been largely superseded by
petroleum products and by synthetic materials. Some organic substances such as lard oil
and sperm oil are still in use as additives because of their special lubricating properties.
Petroleum lubricants are predominantly hydrocarbon products extracted from fluids that
occur naturally within the Earth. They are used widely as lubricants because they possess a
combination of the following desirable properties:
1. availability in suitable viscosities
2. low volatility
3. inertness (resistance to deterioration of the lubricant)
4. corrosion protection (resistance to deterioration of the sliding surfaces)
5. low cost
However, petroleum lubricants loose their inertness when subjected to elevated
temperatures, such as those encountered in modern engines. This causes deterioration of
the lubricant by oxidation, and leads to formation of gum, varnish and other insoluble
deposits. Therefore in most applications petroleum lubricants have to be frequently
changed, if longevity of the equipment is desired.
Synthetic lubricants generally can be characterized as oily, neutral liquid materials not
usually obtained directly from petroleum but having some properties similar to petroleum
lubricants.
In certain ways they are superior to hydrocarbon products. Some synthetics exhibit greater
stability of viscosity with temperature changes, resistance to scuffing and oxidation, and
fire resistance. Since the properties of different types of synthetics vary considerably, each
synthetic lubricant tends to find a special application. There is NO single synthetic
lubricant type that is ideal for all lubricant applications. Commercial synthetic lubricants
(Motor Oil, Gear Oil) are therefore a blend of several different types of Synthetics as well
as select additives.
Grease
Another form of oily lubricant is grease, a solid or semisolid substance consisting of a
liquid lubricant containing a thickening agent.
The liquid lubricant is made from inedible lard, the rendered fat of waste animal parts, or is
petroleum-derived or synthetic high viscosity oil.
Soaps of aluminum, barium, calcium, lithium, sodium, and strontium are the major
thickening agents. Nonsoap thickeners consist of such inorganic compounds as modified
clays or fine silicas, or such organic materials as arylureas or phthalocyanine pigments.
White grease is made from inedible hog fat and has a low content of free fatty acids.
Yellow grease is made from darker parts of the hog and may include parts used to make
white grease.
Brown grease contains beef and mutton fats as well as hog fats. Fleshing grease is the fatty
material trimmed from hides and pelts. Bone grease, hide grease, and garbage grease is
named according to their origin. In some factories, food offal is used along with animal
carcasses, butcher-shop scraps, and garbage from restaurants for recovery of fats.
Greases of mineral or synthetic origin consist of a thickening agent dispersed in a liquid
lubricant such as petroleum oil or a synthetic fluid. The thickening agent may be soap, an
inorganic gel, or an organic substance. Other additives inhibit oxidation and corrosion,
prevent wear, and change viscosity. The fluid component is the more important lubricant
for clearances between parts that are relatively large, but for small clearances the molecular
soap layers provide the lubrication.
Synthetic grease may consist of synthetic oils containing standard soaps or may be a
mixture of synthetic thickeners, or bases, in petroleum oils. Silicones are greases in which
both the base and the oil are synthetic. Synthetic greases are made in water-soluble and
water-resistant forms and may be used over a wide temperature range. The synthetics can
be used in contact with natural or other rubbers because they do not soften these materials.
Special-purpose greases may contain two or more soap bases or special additives to gain a
special characteristic.
Lubrication by grease may prove more desirable than lubrication by oil under conditions
when:
1. less frequent lubricant application is necessary
2. grease acts as a seal against loss of lubricant and ingress of contaminants
3. less dripping or splattering of lubricant is called for
4. less sensitivity to inaccuracies in the mating parts is needed
Solid lubricants
Definition of solid lubricant: A solid lubricant is a material used as powder or thin film to
provide protection from damage during relative movement and to reduce friction and wear.
Other terms commonly used for solid lubrication include dry lubrication, dry-film
lubrication, and solid-film lubrication. Although these terms imply that solid lubrication
takes place under dry conditions, fluids are frequently used as a medium or as a lubricant
with solid additives
A solid lubricant is a film of solid material composed of inorganic or organic compounds
or of metal. Perhaps the most commonly used solid lubricants are the inorganic compounds
graphite and molybdenum disulfide (MoS2 ) and the polymer material
polytetrafluoroethylene (PTFE).
There are three general kinds of inorganic compounds that serve as solid lubricants:
1. Layer-lattice solids: materials such as graphite and molybdenum disulfide,
commonly called molysulfide, have a crystal lattice structure arranged in layers.
Strong bonds between atoms within a layer and relatively weak bonds between
atoms of different layers allow the lamina to slide on one another. Other such
materials are tungsten disulfide, mica, boron nitride, borax, silver sulfate, cadmium
iodide, and lead iodide. Graphite's low friction is due largely to adsorbed films; in
the absence of water vapor, graphite loses its lubricating properties and becomes
abrasive. Both graphite and molysulfide are chemically inert and have high thermal
stability.
2. Miscellaneous soft solids: a variety of inorganic solids such as white lead, lime,
talc, bentonite, silver iodide, and lead monoxide are used as lubricants.
3. Chemical conversion coatings: many inorganic compounds can be formed on a
metallic surface by chemical reaction. The best known such lubricating coatings are
sulfide, chloride, oxide, phosphate, and oxalate films.
Solid organic lubricants are usually divided into two broad classes:
1. Soaps, waxes, and fats: this class includes metallic soaps of calcium, sodium,
lithium; animal waxes (e.g., beeswax and spermaceti wax); fatty acids (e.g., stearic
and palmitic acids); and fatty esters (e.g., lard and tallow).
2. Polymeric films: these are synthetic substances such as polytetrafluoroethylene
(PTFE also known as Teflon®) and polychlorofluoroethylene. One major advantage
of such film-type lubricants is their resistance to deterioration during exposure to
the elements. For Example: ½" (13mm) thick plates of polymeric film are used in
modern prestressed concrete construction to permit thermal movement of beams
resting atop columns. The long-lived polymeric film plate facilitates such
expansion and contraction of the structural members.
Thin films of soft metal on a hard substrate can act as effective lubricants, if the adhesion
to the substrate is good. Such metals include lead, tin, and indium.
Characteristics of Solid Lubricants
Characteristics: The properties important in determining the suitability of a material for
use as a solid lubricant are discussed below.
(1) Crystal structure. Solid lubricants such as graphite and MoS2 possess a lamellar crystal
structure with an inherently low shear strength. Although the lamellar structure is very
favorable for materials such as lubricants, nonlamellar materials also provide satisfactory
lubrication.
(2) Thermal stability. Thermal stability is very important since one of the most significant
uses for solid lubricants is in high temperature applications not tolerated by other
lubricants. Good thermal stability ensures that the solid lubricant will not undergo
undesirable phase or structural changes at high or low temperature extremes.
(3) Oxidation stability. The lubricant should not undergo undesirable oxidative changes
when used within the applicable temperature range.
(4) Volatility. The lubricant should have a low vapor pressure for the expected application
at extreme temperatures and in low-pressure conditions.
(5) Chemical reactivity. The lubricant should form a strong, adherent film on the base
material.
(6) Mobility. The life of solid films can only be maintained if the film remains intact.
Mobility of adsorbates on the surfaces promotes self-healing and prolongs the endurance of
films.
(7) Melting point. If the melting point is exceeded, the atomic bonds that maintain the
molecular structure are destroyed, rendering the lubricant ineffective.
(8) Hardness. Some materials with suitable characteristics, such as those already noted,
have failed as solid lubricants because of excessive hardness. A maximum hardness of 5 on
the Mohs’ scale appears to be the practical limit for solid lubricants.
(9) Electrical conductivity. Certain applications, such as sliding electric contacts, require
high electrical conductivity while other applications, such as insulators making rubbing
contact, require low conductivity.
Applications of Solid Lubrication
Applications of Solid Lubrication. Generally, solid lubricants are used in applications not
tolerated by more conventional lubricants. The most common conditions requiring use of
solid lubricants are:
(1) Extreme temperature and pressure conditions. These are defined as high-temperature
applications up to 1926°C ( 3500°F), where other lubricants are prone to degradation or
decomposition; extremely low temperatures, down to -212°C (-350°F), where lubricants
may solidify or congeal; and high-to-fullvacuum applications, such as space, where
lubricants may volatilize.
(2) As additives. Graphite, MoS2 , and zinc oxide are frequently added to fluids and
greases. Surface conversion coatings are often used to supplement other lubricants.
(3) Intermittent loading conditions. When equipment is stored or is idle for prolonged
periods, solids provide permanent, noncorrosive lubrication.
(4) Inaccessible locations. Where access for servicing is especially difficult, solid
lubricants offer a distinct advantage, provided the lubricant is satisfactory for the intended
loads and speeds.
(5) High dust and lint areas. Solids are also useful in areas where fluids may tend to pick
up dust and lint with liquid lubricants; these contaminants more readily form a grinding
paste, causing damage to equipment.
(6) Contamination. Because of their solid consistency, solids may be used in applications
where the lubricant must not migrate to other locations and cause contamination of other
equipment, parts, or products.
(7) Environmental. Solid lubricants are effective in applications where the lubricated
equipment is immersed in water that may be polluted by other lubricants, such as oils and
greases.
Advantages of Solid Lubrication
Some advantages of solid lubrication are:
(1) More effective than fluid lubricants at high loads and speeds.
(2) High resistance to deterioration in storage.
(3) Highly stable in extreme temperature, pressure, radiation, and reactive environments.
(4) Permit equipment to be lighter and simpler because lubrication distribution systems and
seals are not required.
Disadvantages of Solid Lubrication
(1) Poor self-healing properties. A broken solid film tends to shorten the useful life of the
lubricant.
(2) Poor heat dissipation. This condition is especially true with polymers due to their low
thermal conductivities.
(3) Higher coefficient of friction and wear than hydrodynamically lubricated bearings.
(4) Color associated with solids may be undesirable.
Graphite has a low friction coefficient and very high thermal stability (2000°C [3632°F]
and above). However, practical application is limited to a range of 500 to 600°C (932 to
1112°F) due to oxidation. Furthermore, because graphite relies on adsorbed moisture or
vapors to achieve low friction, use may be further limited. At temperatures as low as
100°C (212°F), the amount of water vapor adsorbed may be significantly reduced to the
point that low friction cannot be maintained. In some instances sufficient vapors may be
extracted from contaminants in the surrounding environment or may be deliberately
introduced to maintain low friction. When necessary, additives composed of inorganic
compounds may be added to enable use at temperatures to 550°C ( 1022°F). Another
concern is that graphite promotes electrolysis. Graphite has a very noble potential of +
0.25V, which can lead to severe galvanic corrosion of copper alloys and stainless steels in
saline waters.
Molybdenum disulfide (MoS2 ). Like graphite, MoS2 has a low friction coefficient, but,
unlike graphite, it does not rely on adsorbed vapors or moisture. In fact, adsorbed vapors
may actually result in a slight, but insignificant, increase in friction. MoS2 also has greater
load-carrying capacity and its manufacturing quality is better controlled. Thermal stability
in nonoxidizing environments is acceptable to 1100°C (2012°F), but in air it may be
reduced to a range of 350 to 400°C (662 to 752°F).
Soft metal films. Many soft metals such as lead, gold, silver, copper, and zinc, possess low
shear strengths and can be used as lubricants by depositing them as thin films on hard
substrates. Deposition methods include electroplating, evaporating, sputtering, and ion
plating. These films are most useful for high temperature applications up to 1000°C
(1832°F) and roller bearing applications where sliding is minimal
Surface treatments commonly used as alternatives to surface film depositions include
thermal diffusion, ion implantation, and chemical conversion coatings.
(a) Thermal diffusion: This is a process that introduces foreign atoms into a surface for
various purposes such as increasing wear-resistance by increasing surface hardness;
producing low shear strength to inhibit scuffing or seizure; and in combination with these
to enhance corrosion-resistance.
(b) Ion implantation: This is a recently developed method that bombards a surface with
ions to increase hardness, which improves wear- and fatigue-resistance.
(c) Chemical conversion coatings: Frequently, solid lubricants will not adhere to the
protected metal surface. A conversion coating is a porous nonlubricating film applied to
the base metal to enable adherence of the solid lubricant. The conversion coating by itself
is not a suitable lubricant.
(4) Polymers: Polymers are used as thin films, as self-lubricating materials, and as binders
for lamellar solids. Films are produced by a process combining spraying and sintering.
Alternatively, a coating can be produced by bonding the polymer with a resin. Sputtering
can also be used to produce films. The most common polymer used for solid lubrication is
PTFE The main advantages of PTFE are low friction coefficient, wide application range of
-200 to 250°C (-328 to 418°F), and lack of chemical reactivity. Disadvantages include
lower load-carrying capacity and endurance limits than other alternatives. Low thermal
conductivity limits use to low speed sliding applications where MoS2 is not satisfactory.
Common applications include antistick coatings and self-lubricating composites.
Methods of Applying Solid Lubricants
There are several methods for applying solid lubricants.
Powdered solids. The oldest and simplest methods of applying solid lubricants are noted
as follows:
(a) Burnishing: Burnishing is a rubbing process used to apply a thin film of dry
powdered solid lubricant such as graphite, MoS2 , etc., to a metal surface. This
process produces a highly polished surface that is effective where lubrication
requirements and wear-life are not stringent, where clearance requirements must be
maintained, and where wear debris from the lubricant must be minimized. Surface
roughness of the metal substrate and particle size of the powder are critical to ensure
good application.
(b) Hand rubbing: Hand rubbing is a procedure for loosely applying a thin coating of
solid lubricant.
(c) Dusting: Powder is applied without any attempt to evenly spread the lubricant.
This method results in a loose and uneven application that is generally unsatisfactory.
(d) Tumbling:. Parts to be lubricated are tumbled in a powdered lubricant. Although
adhesion is not very good, the method is satisfactory for noncritical parts such as
small threaded fasteners and rivets.
(e) Dispersions: Dispersions are mixtures of solid lubricant in grease or fluid
lubricants. The most common solids used are graphite, MoS2 , PTFE, and Teflon®.
The grease or fluid provides normal lubrication while the solid lubricant increases
lubricity and provides extreme pressure protection. Addition of MoS2 to lubricating
oils can increase load-carrying capacity, reduce wear, and increase life in roller
bearings, and has also been found to reduce wear and friction in automotive
applications. However, caution must be exercised when using these solids with
greases and lubricating fluids. Grease and oil may prevent good adhesion of the solid
to the protected surface. Detergent additives in some oils can also inhibit the wearreducing
ability of MoS2 and graphite, and some antiwear additives may actually
increase wear. Solid lubricants can also affect the oxidation stability of oils and
greases. Consequently, the concentration of oxidation inhibitors required must be
carefully examined and controlled. Aerosol sprays are frequently used to apply solid
lubricant in a volatile carrier or in an air-drying organic resin. However, this method
should be limited to short-term uses or to light- or moderate-duty applications where
thick films are not necessary. Specifications for solid lubricant dispersions are not
included in this manual. Before using dispersions, users should become familiar with
their applications and should obtain information in addition to that provided in this
manual. The information should be based on real-world experiences with similar or
comparable applications.
Self-Lubricating Composites
Self-lubricating composites: The primary applications for self-lubricating composites
include dry bearings, gears, seals, sliding electrical contacts, and retainers in roller
bearings. Composites may be polymer, metal-solid, carbon and graphite, and ceramic and
cermets.
Polymer Lubrication
Polymer Lubrication: The low thermal conductivity of polymers inhibits heat
dissipation, which causes premature failure due to melting. This condition is exacerbated if
the counterface material has the same or similar thermal conductivity. Two polymers in
sliding contact will normally operate at significantly reduced speeds than a polymer against
a metal surface. The wear rate of polymer composites is highly dependent upon the surface
roughness of the metal counterfaces. In the initial operating stages, wear is significant but
can be reduced by providing smooth counterfaces. As the run-in period is completed, the
wear rate is reduced due to polymer film transfer or by polishing action between the sliding
surfaces. Environmental factors also influence wear rate. Increased relative humidity
inhibits transfer film formation in polymer composites such as PTFE, which rely on
transfer film formation on counterfaces. The presence of hydrocarbon lubricants may also
produce similar effects. Composites such as nylons and acetals, which do not rely on
transfer film formation, experience reduced wear in the presence of small amounts of
hydrocarbon lubricants.
Metal-Solid Lubrication
Metal-solid Lubrication: Composites containing lamellar solids rely on film transfer to
achieve low friction. The significant amount of solids required to improve film transfer
produces a weak composite with reduced wear life. Addition of nonlamellar solids to these
composites can increase strength and reduce wear. Various manufacturing techniques are
used in the production of metal-solid composites. These include powder metallurgy,
infiltration of porous metals, plasma spraying, and electrochemical code position. Another
fabrication technique requires drilling holes in machine parts and packing the holes with
solid lubricants. One of the most common applications for these composites is selflubricating
roller bearing retainers used in vacuum or high temperatures up to 400°C
(752°F). Another application is in fail-safe operations, where the bearing must continue to
operate for a limited time following failure of the normal lubrication system.
Carbon and Graphites
Carbon and graphites: The primary limitations of bulk carbon are low tensile strength and
lack of ductility. However, their high thermal and oxidation stabilities at temperatures of
500 to 600°C (932 to 1112°F) (higher with additives) enable use at high temperatures and
high sliding speeds. For graphitic carbons in dry conditions, the wear rate increases with
temperature. This condition is exacerbated when adsorbed moisture inhibits transfer film
formation. Furthermore, dusting may also cause failure at high temperatures and sliding
speeds. However, additives are available to inhibit dusting.
Ceramics and Cemets
Ceramics and cermets. Ceramics and cermets can be used in applications where low wear
rate is more critical than low friction. These composites can be used at temperatures up to
1000°C (1832°F). Cermets have a distinct advantage over ceramics in terms of toughness
and ductility. However, the metal content tends to reduce the maximum temperature limit.
Solid lubricant use with bulk ceramics is limited to insertion in machined holes or recesses.
Gaseous lubricants
Lubrication with a gas is analogous in many respects to lubrication with a liquid,
since the same principles of fluid-film lubrication apply. Although both gases and liquids
are viscous fluids, they differ in two important particulars. The viscosity of gases is much
lower and the compressibility much greater than for liquids. Film thicknesses and load
capacities therefore are much lower with a gas such as air. In equipment that handles gases
of various kinds, it is often desirable to lubricate the sliding surfaces with gas in order to
simplify the apparatus and reduce contamination to and from the lubricant. The list of
gases used in this manner is extensive and includes air, steam, industrial gases, and liquidmetal
vapors.
LUBRICATION REZIMES
Untuk sistim pelumasan yang menggunakan pelumas cair, maka kondisi sistim
pelumasannya dapat dibagi menjadi 5 daerah pelumasan yaitu :
1) Solid Contact,
2) Boundary Lubrication,
3) Mixed Lubrication,
4) Hydrodynamic Lubrication
Kondisi yang mempengaruhi jenis pelumasan ini adalah beban, kecepatan dan
viskositas pelumas. Kurva Stribeck Curve yang menunjukkan hubungan antara friction
coefficient dan sliding speed, oil viscosity and load juga digunakan untuk menandai daerah
pelumasan.tersebut, seperti terlihat pada gambar dibawah.
Solid Contact
Solid Contact is a stationary condition where there is intimate contact between two
surfaces. They are interlocked by the surface roughness on each. The Friction Coefficient
is at its maximum. The value of this condition is expressed as Static Coefficient of Friction.
It is also called "Stiction", because the two surfaces literally stick to each other. The higher
is the Static Coefficient of Friction or Stiction the more force it requires to move the two
surfaces in relation to each other. Because there is no movement, there is no Wear.
Because the two surfaces are stationary and interlocked by the surface roughness there is
no Separation between the two surfaces.
Solid Contact condition are Velocity NONE, Friction MAXIMUM, Wear NONE,
Separation NONE
Boundary Lubrication
Boundary Lubrication occurs when there is slow movement and when the two
bearing surfaces are no longer interlocked but also not completely separated. The peaks of
the surface roughness hit each other and as a consequence high Friction and high Wear
results. Such lubrication condition exists during start-up.
Boundary Lubrication condition are Velocity LOW , Friction HIGH, Wear HIGH,
Separation Less than Surface Roughness.
Mixed Lubrication (Elastohydrodynamic Lubrication)
Mixed Lubrication occurs when lubricant film is so thin or load so high that the
lubricant can not completely separate the two bearing surfaces. High load causes
elastodeformation of the surfaces, and increase viscosity of the lubricant. Some minimal
surface roughness contact occurs and this causes low Wear. As the Separation distance
between the two bearing surfaces increases the Friction Coefficient rapidly decreases.
Mixed Lubrication condition are Velocity MODERATE , Friction MODERATE,
and rapidly Decreasing, Wear LOW, Separation Equal to Surface Roughness
Hydrodynamic Lubrication
Hydrodynamic Lubrication occurs when the bearing surfaces are completely
separated by an oil film that is thicker than the surface roughness. Under such condition the
Friction is low and is affected only by the Viscosity of the Oil. Because there is no contact
between the bearing surfaces there is no Wear. As the sliding velocity is increasing the Oil
Viscosity causes slight increase in the Coefficient of Friction
Hydrodynamic Lubrication are condition , Velocity HIGH, Friction LOW, Wear
NONE, Separation More than Surface Roughness
Sol Lubrication
Sol Lubrication occurs when the bearing surfaces are completely separated by an
oil film that contains colloidal particles which are larger in diameter than the surface
roughness. Under such condition the Friction is low and is affected only by the Viscosity
of the Sol. Because there is no contact between the bearing surfaces there is no Wear. As
the sliding velocity is increasing the Sol Viscosity causes slight increase in the Coefficient
of Friction.
Sol Lubrication condition are Velocity NONE to HIGH, Friction LOW, Wear
NONE, Separation More than Surface Roughness
Stribeck Curve comparison between conventional and Sol Lubrication.
Key Features:
Much lower start up Friction Coefficient with no "Stick-Slip" effec
Gradual decline in Friction Coefficient to minimum friction point
Gradual increase in Friction Coefficient from minimum friction point
Returning now to oil lubrication it can been seen that the relative speed, load and
oil viscosity are all related and that to carry an increased load and the same speed, or same
load at a slower speed the oil viscosity needs to be higher. This is why oils are blended to
different viscosities.
As well as the selection of the correct viscosity the choice of base oil can play an
important part in making sure friction is minimised. Under pressure fluids the oil
molecules try to align in such a way as to reduce space they occupy this results in an
increased viscosity. The change of viscosity with pressure (p/v relationship) depends on
the type of oil. For example, paraffinnic oils thicken very quickly to become waxes under
certain conditions where as silicone oils have a very poor p/v curve and therefore should
not be used in high load applications.
2.3 Lubricant Viscosity
Viscosity is one of the most important properties of a lubricating oil. It is one factor
responsible for the formation of lubricating films under both thick and thin film conditions.
Viscosity affects heat generation in bearings, cylinders and gears due to internal fluid
friction. It affects the sealing properties of oils and the rate of oil consumption. It
determines the ease with which machines can be started at various temperatures,
particularly cold temperatures. The satisfactory operation of any given piece of equipment
depends on using an oil with the proper viscosity at the expected operating conditions.
The basic concept of viscosity is
shown in the figure, where a plate is being
drawn at uniform speed over a film of oil.
The oil adheres to both the moving and
stationary surfaces. Oil in contact with the
moving surface travels at the same velocity,
V, as that surface, while oil in contact with
the stationary surface is at zero velocity. In
between, the oil film can be visualized as
many layers, each being drawn by the layer
above it at a fraction of velocity V
proportional to its distance above the
stationary plate.
A force F must be applied to the moving plate to overcome the friction between the
fluid layers. Since this friction is related to viscosity, the force necessary to move the plate
is proportional to viscosity. Viscosity can be determined by measuring the force required to
overcome fluid friction in a film of known dimensions. Viscosity determined in this
manner is called dynamic or absolute viscosity.
Dynamic viscosity is usually reported in poise (P) or centipoise (cP, where 1 cP =
0.01 P), or in SI units as pascal-seconds (Pa-s, where 1 Pa-s = 10 P). Dynamic viscosity,
which is a function of only the internal friction of a fluid, is the quantity used most
frequently in bearing design and oil flow calculations.
Because it is more convenient to measure viscosity in a manner such that the
measurement is affected by oil density, kinematic viscosity is normally used to
characterize lubricants. Kinematic viscosity of a fluid equals its dynamic viscosity divided
by its density, both measured at the same temperature and in consistent units. The most
common units for reporting kinematic viscosity are stokes (St) or centistokes (cSt, where 1
cSt = 0.01 St), or in SI units as square millimeters per second (mm2/s, where 1 mm2/s = 1
cSt).
Dynamic viscosity in centipoise can be converted to kinematic viscosity in
centistokes by dividing by the fluid density in grams per cubic centimeter (g/cm3) at the
same temperature. Kinematic viscosity in square millimeters per second can be converted
to dynamic viscosity in pascal-seconds by multiplying by the density in grams per cubic
centimeter and dividing the result by 1000.
In summary,
2 cm
dynes
Area
Force
Shear Rate = = 1
Gap
Fluid velocity
Shear Rate − = = = s
cm
s
cm
1 P
s
cm
dynes
Shear Rate
Shear Stress
Absolute viscosity 1
2
= = =
−
1 P = 100 cP 100 P = 1 Pa-s
1 Stoke
Densitye
Absolute Vis
KInematic Viscosity = ==
Other viscosity systems, including Saybolt, Redwood, and Engler, have also been
used because of their familiarity to many people. The instruments developed to measure
viscosity in these systems are rarely used. Most viscosity determinations are made in
centistokes and converted to values in other systems.
The viscosity of any fluid changes with temperature, increasing as temperature
decreases, and decreasing as temperature rises. Viscosity may also change with a change in
shear stress or shear rate.
To compare petroleum base oils with respect to viscosity variations with temperature,
ASTM Method D 2270 provides a means to calculate a viscosity index (VI). This is an
arbitrary number used to characterize the variation of kinematic viscosity of a petroleum
product with temperature. The calculation is based on kinematic viscosity measurements at
40 and 100°C. For oils of similar kinematic viscosity, the higher the viscosity index, the
smaller the effect of temperature.
The benefits of higher VI are: 1. Higher viscosity at high temperature, which results in
lower engine oil consumption and less wear. 2. Lower viscosity at low temperature, which
for an engine oil may result in better starting capability and lower fuel consumption during
warm-up.
The measurement of absolute viscosity under realistic conditions has replaced the
conventional viscosity index concept in evaluating lubricants under operating conditions.
Another factor in viscosity measurements is the effect of shear stress or shear rate. For
certain fluids, referred to as Newtonian fluids, viscosity is independent of shear stress or
shear rate. When viscosity is affected by changes in shear stress/shear rate, the fluid is
considered non-Newtonian.
Kinematic viscosity measurements are made at a low shear rate (100 s-1). Other methods
are available to measure viscosity at shear rates that simulate the lubricant environment
under actual operating conditions. Different instruments used to measure kinematic
viscosity are:
1. Capillary Viscometers measure the flow rate of a fixed volume of fluid through a small
orifice at a controlled temperature. The rate of shear can be varied from near zero to 106 s-1
by changing capillary diameter and applied pressure. Types of capillary viscometers and
their mode of operation are:
Glass Capillary Viscometer — Fluid passes through a fixed-diameter orifice under
the influence of gravity. The rate of shear is less than 10 s-1. All kinematic viscosities of
automotive fluids are measured by capillary viscometers.
High-Pressure Capillary Viscometer — Applied gas pressure forces a fixed volume
of fluid through a small-diameter glass capillary. The rate of shear can be varied up to 106
s-1. This technique is commonly used to simulate the viscosity of motor oils in operating
crankshaft bearings. This viscosity is called high-temperature high-shear (HTHS) viscosity
and is measured at 150°C and 106 s-1. HTHS viscosity is also measured by the Tapered
Bearing Simulator (see below).
2. Rotary Viscometers use the torque on a rotating shaft to measure a fluid's resistance to
flow. The Cold Cranking Simulator (CCS), Mini-Rotary Viscometer (MRV), Brookfield
Viscometer and Tapered Bearing Simulator (TBS) are all rotary viscometers. Rate of shear
can be changed by changing rotor dimensions, the gap between rotor and stator wall, and
the speed of rotation.
Cold Cranking Simulator — The CCS measures an apparent viscosity in the range
of 500 to 200,000 cP. Shear rate ranges between 104 and 105 s-1. Normal operating
temperature range is 0 to -40°C. The CCS has demonstrated excellent correlation with
engine cranking data at low temperatures. The SAE J300 viscosity classification specifies
the low-temperature viscometric performance of motor oils by CCS limits and MRV
requirements.
Mini-Rotary Viscometer (ASTM D 4684) — The MRV test, which is related to the
mechanism of pumpability, is a low shear rate measurement. Slow sample cooling rate is
the method's key feature. A sample is pretreated to have a specified thermal history which
includes warming, slow cooling, and soaking cycles. The MRV measures an apparent yield
stress, which, if greater than a threshold value, indicates a potential air-binding pumping
failure problem. Above a certain viscosity (currently defined as 60,000 cP by SAE J 300),
the oil may be subject to pumpability failure by a mechanism called "flow limited"
behavior. An SAE 10W oil, for example, is required to have a maximum viscosity of
60,000 cP at -30°C with no yield stress. This method also measures an apparent viscosity
under shear rates of 1 to 50 s-1.
Brookfield Viscometer — Determines a wide range of viscosities (1 to 105 P) under
a low rate of shear (up to 102 s-1). It is used primarily to determine the low-temperature
viscosity of automotive gear oils, automatic transmission fluids, torque converter and
tractor fluids, and industrial and automotive hydraulic fluids. Test temperature is held
constant in the range -5 to -40°C.
The Scanning Brookfield technique measures the Brookfield viscosity of a sample as it is
cooled at a constant rate of 1°C/hour. Like the MRV, this method is intended to relate to an
oil's pumpability at low temperatures. The test reports the gelation point, defined as the
temperature at which the sample reaches 30,000 cP. The gelation index is also reported,
and is defined as the largest rate of change of viscosity increase from -5°C to the lowest
test temperature. This method is finding application in engine oils, and is required by
ILSAC GF-2.
Tapered Bearing Simulator — This technique also measures high-temperature
high-shear rate viscosity of motor oils (see High Pressure Capillary Viscometer). Very
high shear rates are obtained by using an extremely small gap between the rotor and stator
wall.
Physical requirements for both crankcase oils and gear lubricants are defined by SAE J300.
Properties of Fluid Lubricants
Properti pelumas yang dapat diukur cukup banyak Dibawah ini adalah beberapa
properti pelumas yang biasanya ditonjolkan pada karakteristik pelumas komersial.
Viscosity
Of all the properties of fluid lubricants, viscosity is the most important, since it
determines the amount of friction that will be encountered between sliding surfaces and
whether a thick enough film can be built up to avoid wear from solid-to-solid contact.
Viscosity customarily is measured by a viscometer, which determines the flow rate of the
lubricant under standard conditions; the higher the flow rate, the lower the viscosity. The
rate is expressed in centipoises, reyns, or seconds Saybolt universal (SSU) depending,
respectively, upon whether metric, English, or commercial units are used. In most liquids,
viscosity drops appreciably as the temperature is raised. Since little change of viscosity
with fluctuations in temperature is desirable to keep variations in friction at a minimum,
fluids often are rated in terms of viscosity index. The less the viscosity is changed by
temperature, the higher the viscosity index.
Pour point
The pour point, or the temperature, at which a lubricant ceases to flow, is important
in appraising flow properties at low temperature. As such, it can become the determining
factor in selecting one lubricant from among a group with otherwise identical properties.
Flash point
The flash point, or the temperature, at which a lubricant momentarily flashes in the
pressure of a test flame, aids in evaluating fire-resistance properties. Like the pour-point
factor, the flash point may in some instances become the major consideration in selecting
the proper lubricant, especially in lubricating machinery handling highly flammable
material.
Oiliness
Oiliness generally connotes relative ability to operate under boundary lubrication
conditions. The term relates to a lubricant's tendency to wet and adhere to a surface. There
is no formal test for the measurement of oiliness; determination of this factor is chiefly
through subjective judgment and experience. The most desirable lubricant for a specific
use need not necessarily be the oiliest; e.g., long-fiber grease, which is low in oiliness as
compared with machine oils, is usually preferable for packing rolling bearings.
Neutralization number
The neutralization number is a measure of the acid or alkaline content of new oils
and an indicator of the degree of oxidation degradation of used oils. This value is
ascertained by titration, a standard analytical chemical technique, and is defined as the
number of milligrams of potassium hydroxide required to neutralize one gram of the
lubricant.
Penetration number
The penetration number, applied to grease, is a measure of the film characteristics
of the grease. The test consists of dropping a standard cone into the sample of grease being
tested. Gradations indicate the depth of penetration: the higher the number, the more fluid
the grease.
Beberapa properti yang lain untuk menunjukkan kualitas pelumas, indek viskositas,
warna, kestabilan terhadap oksidasi.
Indek viskositas
Suatu angka empiris yang menunjukkan efek perubahan temperatur terhadap viskositas
minyak lumas. Viskositas akan naik bila temperatur naik, dan sebaliknya. Perubahan ini
tidak sama untuk jenis minyak lumas. Indek viskositas ditentukan dengan cara
perbandingan angka viskositas yang ditentukan pada temperatur 100°F dan 210 °F.
Warna
Warna pada pelumas baru menunjukkan tingkat refenery, warna pada pelumas bekas
menunjukkan tingkat kontaminasi.
Kestabilan Oksidasi
Minyak lumas seperti hidrokarbon yang lain akan mengalami oksidasi jika dikontakan
dengan udara pada temperatur tinggi. Reaksi oksidasi minyak lumas menghasilkan
senyawa asam organik dan peroksida yang menyebabkan perubahan sifat-sifat pelumas
seperti kenaikan viskositas, keasaman, endapan dll.
PERANAN ADITIF
Aditif dapat didefinisikan sebagai senyawa yang dapat memperbaiki atau
menguatkan spesifikasi atau karateristik minyak lumas dasar oil. Beberapa aditif bersifat
multiguna dapat memperbaiki beberapa karakteristik minyak dasar, sementara beberapa
aditif lainnya berfungsi sebagai pelengkap. Beberapa aditif utama dapat diklasifikasikan
sebagai berikut.
Memperbaiki sifat minyak dasar
– Viscosity Index Improver
– Pour Point Depressant
– Antifoamants
Memberikan PROPERTY baru kepada minyak dasar
– Antiwear/EP agents (reduce mechanical wear)
– Detergents (reduce: corrosive wear, deposits, sludge
– Dispersants (reduce: deposits, sludge)
– Antirust
Memperpanjang umur
– Antioxidants
Viscosity Index Improvers
Mempengaruhi hubungan viscosity-temperatur , menurunkan penurunan viskositas
jika suhu naik, dan menaikan viskositas jika suhu turun. Biasanya berupa polimer , seperti
poly-metacrylates, etylen-propylen copolimers (OCP), styrenic copolimers, poly-isoprenes
How they work
Low temperatures High temperatures
At low temperatures, viscosity index improvers are in a “wrapped”
position and do not make much resistance to the oil flow.
At high temperatures, they naturally “unwrap”and create
more resistance to oil flow.
Thickening power Ukuran efektifitas aditif dalam kemampuan memodifikasi
viskositas. Makin efektif berarti makin sedikit jumlah VII yang dibutuhkan untuk
memodifikasi viskositas. Diukur dengan cara menambahkan sejumlah tertentu aditif pada
minyak referensi dan mengukur perubahan viskositasnya.
Shear stability
Viscosity Index Improvers, sebagai molekul yang panjang, selama pemakaian bisa
putus oleh gaya mekanik kuat.. Oleh karena itu pelumas yang mengandung VII dapat
kehilangan viskositas selama pemakaian. Good VII minimize this phenomena
Thickening power semakin besar dengan naiknya berat molekul, namun makin besar
molekul umurnya main pendek. Thickening power and shear stability are in conflict.
VII producer harus merupakan kompromi keduanya.
Pour Point Depressants ( PPD)
PPD dapat mencegah pembentukan krital pada suhu rendah. Contoh PPD adalah
poly-metacrilates, etylen vynil-acetate copolimers, poly-fumarates. Penekanan Pour point
tergantung terutama pada karakterisitik base oil dan konsentrasi polimer. PPD lebih efektif
jika dipergunakan dalam minyak dasar viskositas rendah (SN 80, SN 150). Mereka
memiliki batas konsentrasi efektif yaitu sekitar 0.1 to 1%.
Detergents
Molekul deterjen dapat digambarkan sbb :
Detergents/Dispersants. How they work
The polar part of the molecule adheres to the metallic surfaces andavoids the formation of
depositsor it adheres to insolubles, thus avoiding their agglomeration
Dispersants
Menjaga senyawa (insolubles, sludge), tetap dalam suspensi, menghindarkan
aglomerasi dan presipitasi. Berfungsi mengendalikan deposit yang terjadi pada suhu tinggi.
Types: succinimides and succinicesters, mannich bases. Dalam paket pelumas mesin
kandungannya 50% dari total additif., dan merupakan aditif utama yang berfungsi
mendispersikan sludge dalam mesin bensin, atau pada mesin diesel mendispesikan soot
(jelaga) mencegah kenaikan viskositas .
Antiwear – EP
Dalam kondisi beban medium-tinggi, aditif antiwear (EP) bereaksi dengan
permukaan logam membentuk lapisan yang memiliki friction coefficient.rendah .Types:
Zinc diackyl dithio phosphates, Sulfur-Phosphorous Compounds, Clorurated Paraffins,
Organic sulphur compounds, Zinc Dialkyl Dithio Phosphates (ZnDTP). Aditif ini juga
merupakan antioksidan yang baik. Sejak pemakaian catalytic converter penggunaan
ZnDTP dipertanyakan karena, fosfor yang ada dalam ZnDTP meracuni catalis. Hal ini
terjadi karena pelumas yang terbakar bersama bensin bercampur dengan gas buang. Belum
adanya aditif pengganti yang se efficient ZDDP’s, maka hanya bisa dilakukan
pengurangan phosphorous dalam minyak lumas.
Antioxidants
Berfungsi menghentikan atau memperlambat reaksi kimia antara molekul
hidrocarbon dalam pelumas dan oksigen dari udara. Oksidasi merupakan mekanisme
utama yang bertanggung jawab pada kerusakan pelumas, berupa pembentukan varnish,
sludge, soot and corrosive wear, dan menyebabkab kenaikan viscosity mengubah rheology
pelumas.
Corrosion Inhibitors – Antirust
Berfungsi terutama menciptakan barier fisik pada permukaan logam mencegah
serangan senyawa korosif (air, asam hasil oksidasi, oxidator) pada permukaan logam.
Types: dodecyl succinic acid, phosphoric esters, amines, imidazolines, sulfur derivatives
Antifoamants
Bekerja memodifikasi permukaan pelumas pada antar muka udara-minyak. Sering
mereka adalah senyawa yang dapat terdispersi lebih banyak diudara dari pada yang larut
dalam minyak. Types: sylicons, poliacrilate.
Paket Aditif
Kampuran komplek aditif yang ditambahkan ke dalam minyak dasar untuk
mendapatkan tingkat kinerja yang diinginkan. Interaksi aktara beberapa aditif yang
berbeda dapat bersifat sinergis ataupun antagonis. Pengetahuan tentang interaksi ini
merupakan proprietary know how.
Engine Oil package
Dispersant 35-60%
Detergent 25-35%
Antiwear 15-20%
Others 5-15%
3. BASE OIL
3.1 FUNGSI PELUMAS
Fungsi utama suatu pelumas adalah untuk mengendalikan friksi dan keausan,
namun pelumas juga melakukan beberapa fungsi lain yang bervariasi tergantung dimana
pelumas tersebut diaplikasikan..
Jumlah dan karakter pelumas menentukan besarnya friksi. Pelumasan lapisan fluida
bisa memberikan pengurangan friksi 200 kali lebih kecil dibandingkan tanpa pelumas.
Pada pelumasan lapisan fluida, friksi berbanding lurus dengan viskositas pelumas. Pada
kondisi pelumasan batas pengaruh viskositas menjadi kurang penting, bergeser sifat kimia
dari pelumas menjadi lebih penting.
Keausan terjadi pada permukaan disebabkan oleh abrasi, korosi dan adesi. Pelumas
yang baik juga dituntut untuk membantu mengurangi keausan ini. Keausan adesi dan
abrasi dikurangi dengan cara pelumasan lapisan fluida, agar permukaan terpisah
sempurna dari kontak asperiti dan kontaminan.
Pencegahan Korosi
Peranan pelumas dalam mencegah korosi , pertama saat mesin idle, pelumas
berfungsi sebagai preservative.Pada saat mesin bekerja pelumas melapisi bagian mesin
dengan lapisan pelindung yang mengandung aditif untuk menetralkan bahan korosif.
Kemampuan pelumas mengendalikan korosi tergantung pada ketebalan lapisan fluida dan
komposisi kimianya.
Heat Removal
Another important function of a lubricant is to act as a coolant, removing heat
generated by either friction or other sources such as combustion or contact with hightemperature
substances. In performing this function, the lubricant must remain relatively
unchanged. Changes in thermal and oxidative stability will materially decrease a lubricant's
efficiency in this regard. Additives are generally employed to solve such problems.
Suspension of Contaminants
The ability of a lubricant to remain effective in the presence of outside
contaminants is quite important. Among these contaminants are water, acidic combustion
products, and particulate matter. Additives are generally the answer in minimizing the
adverse effects of contaminants
Fungsi Lainnya
Various lubricants are employed as hydraulic fluids in fluid transmission devices.
Others can be used to remove contaminants in mechanical systems. In specialized
applications such as transformers and switchgear, lubricants with high dielectric constants
act as electrical insulators. For maximum insulating properties, a lubricant must be kept
free of contaminants and water.
Lubricants also act as shock-damping fluids in energy-transferring devices (e.g., shock
absorbers) and around such machine parts as gears that are subjected to high intermittent
loads.
3.2 KARAKTERISIK PENTING UNTUK PELUMAS CAIR
Beberapa sifat penting yang sangat dibutuhkan agar minyak lumasi dapat berfungsi
dengan baik adalah :
1. Low volatility atau tidak mudah menguap, terutama pada kondisi operasi. Volatilitas
suatu minyak lumas penting sekali dalam pemilihan jenis pelumas dasar sesuai dengan
pemakaian. Sifat ini tidak dapat diperbaiki dengan penambahan aditif.
2. Fluiditas atau sifat mengalir dalam daerah suhu operasi. Karakterisitik aliran
dipengaruhi sebagian besar oleh minyak dasar. Fluiditas dapat diperbaiki dengan aditif >
Pour point depressants untuk memperbaiki aliran pada suhu, viscosity modifiers untuk
memperbaiki aliran pada suhu tinggi.
3. Stabilitas selama periode pemakaian. Sebagian sifat ini ditentukan oleh sifat minyak
dasar, namun terutama ditentukan oleh aditif yang memperbaiki stabilitas..
Stabilitas pelumas sangat ditentukan oleh kondisi lingkungan seperti temperatur, potensial
oksidasi dan kontaminasi dengan air, fraksi bahan bahan yang tak terbakar, dan asam-asam
korosif.membatasi umur pelumas. Aditif sangat berperan menaikkan kinerja dan umur
pelumas.
4. Kompatibilitas atau kecocokan dengan bahan lain dalam sistim. Kompatibilitas pelumas
dengan seals, bearings, clutch plates dll., sebagian ditentukan oleh sifat minyak dasar.
Namun aditif juga dapat memiliki pengaruh besar memperbaiki sifat ini.
3.3 PELUMAS PETRO (MINERAL OIL)
Minyak bumi terbentuk beberapa ribu tahun yang lalu, berasal dari sisa-sisa
tanaman dan binatang kecil yang hidup di air mengendap bersama dengan lumpur dan
pasir didasar laut. Endapan tersebut menerima tekanan dan tempertatur tinggi akibat
tekanan dari lapisan yang terakumulasi, melalui transformasi kimia terbentuklah
hidrokarbon dan senyawa lain dalam minyak mentah.Minyak mentah berpindah,
terakumulasi pada batuan berpori, karena terperangkap oleh batuan kedap. Dibagian bawah
minyak biasanya terdapat lapisan air garam.,
Minyak mentah diperoleh dengan cara membor sumur kedalaman lima mil ke dalam bumi.
Minyak mentah dalam bumi biasanya bertekanan tinggi dan mengandung gas. Gas
dipisahkan dari cairan minyak dan kemudian diolah untuk mendapatkan cairan yang lebih
mudah menguap (volatil) untuk membuat ” "natural gasoline." Gas bisa dijadilkan bahan
bakar atau dikembalikan ke dlalam sumur untuk menjaga agar tekanan sumur minyak tetap
tinggi untuk menaikan perolehan minyak mentah..
Minyak mentah dijumpai dalam berbagai variasi, dari minyak berwarna bening
(mengandung banyak bensin) sampai yang berwarna hitam pekat., mendekat padat seperti
apal. Minyak mentah adalah campuran komplek terdiri dari berbagai hidrokarbon, mulai
metana sampai senyawa yang memiliki lebih dari 50 rantai karbon.
Titik titik didih senyawa hidrokarbon meningkat dengan bertambahnya jumlah atom
karbon :
Components
Approximate Boiling
Range (°C)
Natural Gas Hydrocarbons Below -20
Gasoline Components 30 to 200
Diesel and Home Heating Oils 200 to 350
Lubricating Oils and Heavier Fuels Above 350
Senyawa hidrokarbon berat tidak dapat di uapkan karena akan terdekomposisi jika
dipanaskan diatas temperatur distilasi normal. Molekulnya akan patah membentuk gas,
bensin, dan bahan bakar ringan. Atau ada juga yang bergabung membentuk molekul besar,
seperti pada pembentukan residu karbon, disebut "coke."
Minyak mentah juga mengandung berbagai senyawa seperti sulfur, sulfur, nitrogen,
and oxygen; metal seperti vanadium and nickel; water; and salts. Semua senyawa tersebut
dapat menyebabkan persoalan pada proses pengolahan. Untuk mengurangi atau
menghilangkannya menambah beban biaya proses.
Tahap pertama proses pengolahan minyak biasanya adalah pengambilan garam
(desalting), diikuti oleh pemanasan dalam furnace, dimana minyak diuapkan parsial.
Campuran gas-cair panas memasuki kolom fraksionasi yang beroperasi pada tekanan
sedikit diatas atmosfer. Alat ini memilah-milah hidrokarbon berdasarkan titik didihnya.
Residu berwarna hitam, yaitu suatu campuran hidrokarbon yang lebih berat, keluar
melalui dasar kolom fraksionasi.
Karena residu terdekomposisi (pecah secara kimia) pada temperatur 700°F (371°C)
tekanan atmosferik, maka proses fraksionasi residu dilakukan dalam tekanan rendah ataui
vakum. Pengurangan tekanan dapat menurunkan titik didih komponen. Produk bawah
kolom fraksionasi vakum biasanya digunakan sebagai aspal ataupun diproses lagi untuk
menghasilkan “bright stocks.” Fraksi minyak bumi yang diperoleh langsung dari distilasi
disebut produk "straight run".
Minyak lumas dapat diperoleh dari berbagai sumber minyak bumi didunia, oleh karena itu
sifatnya berbeda-beda. Sebagai gambarkan kompleksitas minyak lumas, adalah variasi
yang dapat dimiliki oleh satu molekul hidrokarbon parafinik yang memiliki 25 atom
karbon (titik didih pada daerah minyak lumas) memiliki 52 atom hidrogen dan 37 million
struktur molekul berbeda.
Misalkan beberapa senyawa hidrokarbon naftenik dan aroatik juga memiliki 25 atom
karbon, jumlah variasi strukturnya makin bertambah banyak. Hal ini menjelaskan kenapa
terdapat variasi sifat fisika kimia dan juga unjuk kerja minyak lumas yang dibuat dari
sumber yang berbeda.
PEMBUATAN PELUMAS PETRO
The general principles of lubricant base oil manufacturer use a series of steps to
improve certain desirable lubricant properties. These include:Viscosity Index, Oxidation,
Heat Resistance, Low Temperature Fluidity
Starting from petroleum crude oil, Pembuatan minyak lumas mineral melibat seri proses
pengurangan untuk mengurangi atau menghilangkan komponen yang tidak diinginkan,
menghasilkan minyak dasar yang memenuhi unjuk kerja yang diinginkan. Umumnya
melibatkan tidak kurang dari lima tahap :
1. Separation of lighter boiling materials such as gasoline, jet fuel, diesel, etc.
2. Removal of impurities including aromatics and polar compounds.
3. Distillation to give desired base oil viscosity grades.
4. Dewaxing to improve low temperature fluidity.
5. Finishing to improve oxidation and heat stability.
SOLVENT REFINING PROCESS
This process which was developed in the 1920's attempts to remove the undesirable
components from the feedstock by solvent extraction. Light oils such as gasoline, diesel,
etc., are first separated from the crude oil by atmospheric distillation. The resulting
feedstock is charged to a vacuum Distillation tower where lubricant fractions of specific
viscosity ranges are produced. These fractions are treated individually in a solvent
extraction tower where the solvent is mixed with the lubricant fractions. This extracts up to
80% of the aromatic hydrocarbons, and other undesirable components. After removing the
aromatics, the solvent extracted lube fraction is dewaxed to improve lower temperature
fluidity. Finally, the dewaxed lube fractions are finished to improve their colour and
stability. One common method of finishing is mild hydrotreating. Refer to the diagram
below for a graphical representation of the process.
1. Distilasi vakum, memisahkan residu distilasi atmosferik menjadi beberapa fraksi yang
mewakili berat molekul atau viskositas berbeda dari 90-100 neutralssampai 500
neutrals.(“neutral number” adalah viskositas SUS (Saybolt Unit Second) pada 100°F).
Residu mengandung minyak dasar berat seperti bright stocks (150 to 250 SUS pada
210°F), harus dipisahkan dari asphaltenes dan resins (Proses Propana Deasphalting)
sebelum diproses secara ekstraksi.
2. Ekstraksi (dengan pelarut furfural) memisahkan senyawa aromatik dari senyawa non
aromatik. Furfural dicampur dengan feed, kemudian campuran dibiarkan memisah menjadi
dua fasa, ekstrak dan rafinat. Dua fas tersebut dipisahkan dan pelarutnya dihilangkan dari
masing-masing fasa.
Fasa ekstrak kaya hidrokarbon aromatik, dan fasa rafinat kaya naftenik.and the raffinate
phase is rich in paraffinic hydrocarbons. Proses ekstraksi meningkatkan stabilitas termal
dan oksidatif dibandingkan dengan fraksi sebelum ekstraksi. Disamping itu memperbaiiki
karakterisitik viskositas/temperatur atau memperbaiiki indek viskositas.
3. Wax Removal, dimaksudkan untuk memperbaiki sifat fluiditas atau titik tuang pada
suhu rendah. Methyl ethyl ketone (MEK) dicampur dengan feed, campuran didinginkan
sampai 10 to 20°F (-12 to -6°C) dibawah titik tuang yang diinginkan. Kristak lilin yang
terbentuk dihilangkan dengan filtrasi.
4. Hydrofinishing or clay treatment dimaksudkan untuk memperbaiki warna, stabilitas
oksidasi, stabilitas termal. Hydrofinishing dilakukan dengan melewatkan minyak panas
dan hidrogen melalui katalis. Proses ini menghilangkan senyawa penyebab warna dan
komponen tidak stabil seperti senyawa nitrogen and sulfur compounds. Alternatif lain
adalah clay treatment, juga menghilangkan warna gelap dan molekul tidak stabil.
Selain hydrofinishing, juga digunakan beberapa proses hidrogenasi.
Hydrotreating, proses hidrogenasi ini lebih kuat, kadang diletakan sebelum ekstraksi.
Tujuannya adalah untuk meningkatkan perolehan atau yield ekstraksi dengan cara
mengubah senyawa aromatik menjadi non aromatik agar tetap tinggal di rafinat. Proses
ini juga sekaligus juga merupakan proses desulfurisasi dan juga proses nitrogen removal.
5. Pendekatan yang berbeda total untuk membuat minyak lumas adalah melalui proses
hydrocracking. Prosesini merubah struktur beberapa senyawa dalam feed. Aromatik
diubah menjadi naftenik, cincin senyawa naftenik dibuka, beberapa senyawa naftenik
diputus atau direformasi. Proses reformasi ini menghasilkan molekul yang karakteristik
viskositas/temperaturnya bagus dan memperbaiki stabilitas oksidasi. Proses ini lebih
fleksibel terhadap feed, menghasilkan minyak dasar yang berkualitas.
Inspection Characteristics of Some Finished Petroleum Oils
Specific
Gravity at
60°F
Sulfur
(% wt)
Viscosity
Index
Kinematic Viscosity (cSt) Pour
Point
(°C)
COC
Flash
at 40°C at 100°C (°C)
Source 1
100 Neutral 0.860 0.065 101 20.39 4.11 -13 192
200 Neutral 0.872 0.096 99 40.74 6.23 -20 226
350 Neutral 0.877 0.126 97 65.59 8.39 -18 252
650 Neutral 0.882 0.155 96 117.90 12.43 -18 272
150 Bright Stock 0.895 0.263 95 438.00 29.46 -18 302
Minyak dasar hasil pengilangan memiliki bermacam viskositas . Tabel diatas
menunjukkan beberapa karakteristik produk solvent refining.
Disamping itu ada klasifikasi menurut Indeks Viskositas, sebagai berikut :
HVI (high viscosity index), yaitu minyak lumas dengan indek viskositas >85; MVI
(medium viscosity index), yaitu minyak lumas dengan indek viskositas 30-85; LVI HVI
(high viscosity index), yaitu minyak lumas dengan indek viskositas <30
HYDROTREATING PROCESS
The elimination of aromatics and impurities is accomplishes by chemically reacting the
lubricant feedstock with hydrogen in the presence of a catalyst, under conditions of high
temperature and pressure.
Several different reactions occur in this process, the principle ones being:
• Removal of polar compounds containing sulphur, nitrogen, and oxygen.
• Conversion of aromatic hydrocarbons to saturated cyclic hydrocarbons.
• Breaking up of heavy polycyclo-paraffins to lighter saturated hydrocarbons.
These reactions take place at very high temperatures(400°C) and pressure(3000psi) in the
presence of a catalyst. The hydrocarbon molecules that are formed in the process are very
stable, which make them ideal for use as lubricant base oils.
Refer to the diagram below for a graphical representation of the two stage
HYDROTREATING process. The first stage removes unwanted polar compounds and
converts the unsaturated feedstock into a saturated waxy lube fraction. After separation
into desired viscosity grades, batches of waxy base oils are dewaxed and the passed
through the second stage hydrotreater for additional saturation. This maximizes base oil
stability by removing the remaining traces of polar compounds and un saturates.
. There are significant HydroTreated and Solvent Refined base oils.
The main reason for these differences lies in the virtual elimination of
aromatics(less than 0.5%) using the HydroTreating process. HydroTreated base oils may
therefore be termed"99.5% Pure" In comparison, the aromatic content of Solvent Refined
oils is somewhere around 20%.; so Solvent Refined oils are considered "80%Pure". The
following are the characteristics and significant differences:
COLOUR
All 2-stage Hydrotreated base oils are clear and colourless.
VISCOSITY INDEX(VI)
HydroTreated base oils generally have higher VI's than Solvent Refined oils. As a
result, viscosity drops off less at high temperatures than with Solvent Refined oils.
CARBON RESIDUE
Lower for HydroTreated base oils.
TOTAL ACID NUMBER(TAN)
Lower for HydroTreated base oils.
DEMULSIBILITY
HydroTreated oils will shed water better than Solvent Refined oils.
OXIDATION RESISTANCE
HydroTreated base oils, at equal levels of anti-oxidant treatment, give superior
resistance to oxidation.
HIGH TEMPERATURE STABILITY
Better high temperature stability for HydroTreated oils.
Lube Base Stocks
Lube base stocks (of petroleum origin) continue to constitute a major part of today's
lubricant. These are complex mixtures of paraffinic, aromatics and naphthenic hydrocarbon
type molecules, ranging in carbon number from 14 to 40+. They constitute a very
important segment of the hydrocarbon industry. Manufacture of these base stocks in the
past two decades or so underwent evolutionary changes due to a number of reasons. The
variety of crude oils that need to be processed considerably increased, coupled with the
introduction of new and improved refining processes. Hydroprocessing has emerged to be
the most important routes for this purpose. Different processing configurations involving
replacement of dearomatisation, dewaxing and hydrofinishing steps have been developed.
Hydrocracking / hydroisomerisation enabled the refineries to produce High Viscosity
Index (designated as VHVI or X-HVI) paraffinic base stocks / oils that are comparable in
performance to synthetic base fluids. Paraffinic base stocks are preferentially used to
formulate most of the world's automotive and industrial lubricants, including engine oils,
transmission fluids and gear oils, due to their better oxidation stability, higher viscosity
index and lower volatility relative to comparable viscosity grade naphthenic base oils.
Naphthenic base oils have lower pour points and better solvency characteristics, compared
to paraffinic base oils which makes them, particularly useful in formulating low
temperature, hydraulic oils, refrigeration oils, rubber process oils, metal working oils, as
well as cylinder lubricants for large engines and greases.
Base stocks differ widely in molecular composition, physical and chemical
properties due to the crude source and processing steps used in their manufacture. These
differences in base stock composition, even with similar physical properties can impact the
end use performance of finished lubricants. As such lube base stocks are thus considered to
be non-fungible products in many end use applications. In 1990 the American Petroleum
Institute (API) established a base oil classification system to help marketers to minimize
re-testing costs when blending licensed engine oils with base oils from different
manufacturing sources. The system uses physical and chemical parameters to divide all
base stocks (oils) into five groups as listed in table below :
API - Classification of Base Oils
Group
Saturate wt
%
Sulphur wt % Viscosity Index
I < 90 and/or > 0.03 > 80 to < 120
II ≥ 90 and ≤ 0.03 ≥ 80 to X 120
III ≥ 90 X 0.03 ≥ 120
IV All poly alpha olefins (PAOs)
V All base stocks not included in Groups I-IV
It would be seen from the above data that as one moves from Group I to Group III
base stocks, paraffinicity improves do the volatility characteristics due to shifts in
manufacturing practice and higher isoparaffin contents. Group IV base oil contains all
PAOs, which are used neat and in admixture with mineral base oils to improve lubricants
properties. API Group V contains all other base stocks, including all naphthenic base oils,
medium VI paraffinic stocks and synthetic fluids such as esters, silicones and polyglycols.
The fourth annual edition of 'Lubricants World' has recently published a list of '2002 Base
Oil Refining Facilities' world wide, region wise distribution of which is shown in the table
below :
While Europe and USA have practically the same number of lube plants but differ in over
all capacity. Asia tops the list with 34 plants having practically the same capacity as in
USA. Middle East and Africa two together have 15 lube refineries.
Region Wise Distribution of Global Base Oil Refining Capacity (2002)
Sl.No. Region
Number of
LubeRefineries/
Plants
Total
Capacity(BPD)
1 Canada 4 26500
2 United States 23 218900
3 Latin America 13 59805
4 Europe 24 177444
5 Former Soviet Union 17 259600
6 Asia 34 220533
7 Middle East & Africa 15 49245
8 Australia 3 12679
Total* 133 1024706
BPD = Barrels Per Day Source : Lubricants World 4th Annual Edn. 2002
* Plants with capacities under 3000 BPD particularly in Europe and Asia have not been
individually listed.
World wide base oil demand has risen by more than 10% since 1995, and is
expected to keep growing briskly. Despite over supply plaguing some regions, such as
Europe, new markets are developing for high quality Group II and Group III base oils to
meet more stringent environmental and vehicle performance standards around the world.
These standards are triggering closures or upgrades of Group I plants in the USA. and
planning emphasis of higher-grade base oils elsewhere, particularly Asia.
Synthetic Base Oils
Minyal Lumas sintetis didefinisikan sebagai "Suatu produk yang dibuat melalui
reaksi kimia ari senyawa berat molekul rentah menjadi senyawa berat molekul tinggi yang
dirancang untuk memenuhi sifat yang direncanakan. Ini berbeda dengan minyak lumas
mineral yang terdiri atas banyak komponen dengan komposisi bervariasi tergantung pada
metoda produksi dan sumber minyak mentahnya..
Synthetic basestocks, start from relatively pure and simple chemical building blocks which
are then reacted together or synthesized into new, larger molecules. The resulting synthetic
basestock consists only of the pre-selected molecules and has no undesirable weak links that inhibit
performance. This ability to pre-select or design specific ideal molecules tailored for a given job,
and then create those molecules and only those molecules, opens a whole new world for making
superior basestocks for lubricants. If fact the entire formulation approach is different: instead of
trying to clean up a naturally occurring chemical soup to acceptable levels with a constant eye on
cost, the synthetic molecular engineer is able to focus on optimum performance in a specific
application with the knowledge that he can build the necessary molecules to achieve it. Since
synthetics cost considerably more than petroleum based basestocks, they are generally reserved
for problem applications where conventional oils fail, or where the efficiency benefits of synthetics
recoup the initial cost.
The use of synthetic basestocks to solve lubrication problems is not new. Various synthetics
were developed and used extensively during the second world war to prevent the oil from freezing
in the army tanks during winter combat. After the war, synthetics were found to be essential for
the new jet engines which ran too hot for mineral oils, causing them to burn off rapidly and leave
deposits. These jet engines also had to be able to restart at high altitudes where temperatures
were often -50F, so the oil had to pumpable at very low temperatures as well as surviving the
searing temperatures within the engine. Indeed the modern jet engine would not exist today if not
for the simultaneous development of synthetic basestock technology in the 1950s, and today
virtually every jet engine in the world operates exclusively on synthetic lubricants.
During the 1960s and 70s, synthetics moved steadily into severe industrial applications where they
solved high temperature deposit problems with air compressors and oven conveyor chains, and low
temperature flow problems in arctic climates. New synthetic chemistries emerged to meet and
match every problem industrial users could create, and there were many! Gradually these
expensive high-tech synthetic lubricants were entering the mainstream and taken seriously as they
proved their ability to save money through reduced downtime, less maintenance costs, extended
equipment life, lower energy consumption, and higher productivity. Focus shifted to the total cost
of lubrication, not just the cost of the lubricant, and synthetics were often the winners.
Synthetic automobile motor oils were introduced in the early 1970s with such fantastic performance
claims that they initially turned the auto manufacturers and oil companies against the new
unproven products. While most claims were directionally valid, the level of improvements were
often exaggerated to the point of fostering a "snake oil" reputation. Over the ensuing years, the
true benefits of synthetic motor oils were identified and quantified to industry satisfaction and
include better high temperature stability, excellent low temperature flow characteristics, lower
volatility, increased fuel efficiency, and extended life capability. Today car manufacturers and oil
companies alike readily acknowledge the superior performance of synthetic motor and gear oils,
especially in fleet or severe duty usage. For the average car owner, however, driving conditions are
mild enough for conventional mineral oils to work satisfactorily, which raises the question of
whether synthetic benefits are really needed for passenger cars and worth the higher price tag. In
most cases the combined improvements will repay the higher initial cost, but since these
improvements are not readily perceived by the driver, market penetration remains only a few
percent after nearly thirty years. Synthetic motor oil usage will likely accelerate in future years as
engine builders exploit the benefits in new engine design and ratchet up oil performance through
tighter specifications.
Today the use of synthetic lubricants is accepted, widespread, and rapidly growing as their
capability and cost efficiency benefits become better known worldwide. Jet aircraft use synthetic
oils in the engines, hydraulic systems, instruments and landing gears; compressors use synthetics
in the crankcase and cylinders; refrigeration systems use synthetics with the new environmentally
friendly refrigerants; truck fleets use synthetics in the engine, transmission, and gear box; and the
list goes on and on. Wherever a problem exists with mineral oils or a potential for improved cost
efficiency uncovered, there is a synthetic lubricant ready and able to step in and lower the cost of
total lubrication.
Minyak sintetis tidak hanya berasal dari satu jenis senyawa kimia. Classificationa
of Synthetic Fluids According to Chemical Composition
Synthetic fluids Composition
Synthetic hydrocarbon C, H
Polyalphaolefins
Alkylated aromatics
Monoalkylbenzenes
Dialkylbenzenes
Polyalkylene glycol C, H, O
Carboxylic acid esters C, H, O
Dicarboxylic acid esters
Neopentyl polyesters
Phosphoric acid esters (phosphate esters) C, H, O, P
Silicone oils C, H, O, Si
Silicone oils
Polysilicone oils (sloxanes)
Polyphenylether C, H, O
Polyfluoroalkylether (alkoxyfluoro oils) C, F, O
Chlorofluorocarbons
Chlorotrifluoroethylenes
Polymethacrylate/polyalphaolefine-cooligomers
Dari sekian banyak pelumas sintetik, yang banyak dijual dipasaran adalah :
• Olefin oligomers — Automotive and industrial applications
• Neopentyl polyol esters — Automotive and aircraft applications
• Esters of dibasic acids — Automotive and aircraft applications
• Alkylated aromatics — Automotive and industrial applications
Keempat jenis ini banyak digunakan pada pelumas kendaraan bermotor baik sendirian
maupun sebagai campuran dengan minyak mineral.Tabel dibawah menunjukkan beberapa
karakteristik minyak sintetis tersebut.
Physical Inspection Characteristics of Typical Synthetic Fluids
Fluid
Dynamic
Viscosity
(cP) at -
40°F
Kinematic
Viscosity
(cSt) Viscosity
Index
Pour
Point
(°C)
COC
Flash
(°C)
Temperature
Range (°C)
at
40°C
at
100°C
Olefin Oligomer 2371 18.12 3.96 126 -79 221 -65 to 232
Olefin Oligomer 8176 34.07 6.00 134 -68 243 -65 to 232
Ester of Dibasic Acid
— Dioctyl Sebacate
3450 119.58 — 76 -51 232 -54 to 204
Ester of Trimethylol —
Propane (C7)
2360 15.00 3.50 — < -51 232 -59 to 280
Alkylated Aromatics 9047 29.37 5.10 119 -54 224 -40 to 177
Fluida sintetik lain, namun masih sangat spesifik penggunaannya adalah
polyglycols, phosphate esters, silicones, silicate esters, and polyphenyl ethers.
Secara umum minyak sintetis dapat digunakan dalam daerah temperatur yang lebih lebar
dibandingkan dengan minyak mineral yang sama viskositasnya.
Some of the most common synthetic lubricants are listed below
1. Polyglycol fluids- Polyalkylene Glycol, Polyglycol Ethers, Polyalkalylene Glycol
Ethers
2. Silicones
3. Esters: Diesters (Dibasic Acid Esters)
4. Esters: Polyolesters (Neopentyl Poly Esters)
5. Polymerized alpha olefin: Polyalphaolefin, Olefin Polymers, Olefin Oligomerssynthetic
hydrocarbons
6. Alkylated Aromatics- Dialkylbenzenes- a synthetic hydrocarbon
7. Phosphate Esters
There are many hundreds more types of synthetic lubricants and chemical
variations of these synthetic lubricants. There is also no one specific synthetic lubricant
that is superior in all respects, although a particular synthetic lubricant may possess
certain specific advantages for a specific application. The synthetic lubricants listed in
this book account for the majority of the volume of synthetic lubricant base stocks now
used.
Some of the common applications of each type of synthetic lubricant as well as the general
process that the synthetic is manufactured where applicable are listed below:
Polyglycols
These synthetic fluids were among the earliest used where extremes of temperature were
encountered. The first use of polyglycols was for a water based hydraulic fluid for the U.S.
Navy in 1943 for use in military aircraft so that fires would not result if bullets or shrapnel
severs hydraulic lines.
They have good lubricity, low sludge deposits, high natural viscosity indexes and good
temperature stability. Typical applications include automotive hydraulic brake systems
(ethylene and polyethylene glycol), industrial gear oils, fire resistant fluids (by mixing the
polyglycol with water), greases, metal working fluids and gas compressor oils.
Polyglycols were tested extensively for automobile engines but never developed into
widespread use. Polyglycols are not compatible with petroleum oil. The chemical process
used to manufacture polyglycols is beyond the scope of this book and is highly complex
and one would need to be chemist or engineer to fully understand the process
Silicones
Silicones have high viscosity indexes and high thermal stability as well as excellent low
temperature performance, which makes them good for use in certain greases, torsion
dampers and in automotive brake hydraulic systems. Silicone brake fluids have excellent
temperature stability in newer vehicles, which have high performance brake systems but
they are not nearly as water tolerant as Polyglycol brake fluids. Water gets in brake
systems over a period of time through the hydraulic lines, fittings and breather cap. As
little as 2-3% water in a brake system is enough so that it can cause brake concerns.
Silicone brake fluid and Polyglycol brake fluid are not compatible with each other and
serious brake performance concerns can result if the two are mixed together. Additionally,
the higher the temperature/performance rating of a brake fluid, regardless if it is Polyglycol
or Silicone, the higher the affinity of the brake fluid to absorb water.
Esters: Diesters (dibasic acid esters)
During World War II a range of synthetic oils was developed. Among these, esters of longchain
alcohols and acids proved to be excellent for low temperature lubricants. Following
World War II, the further development of esters was closely linked to the aviation gas
turbine. In the early 1960s, neopolyol esters were used in this application because of their
low volatilities, high flash points and good thermal stabilities.
Diesters are prepared by reacting a dibasic acid with an alcohol containing one reactive
hydroxyl group. Note that the hydrolytic stability of diesters is not as good as mineral oils.
Hydrolytic stability refers to how the lubricant reacts in the presence of water. Hydrolytic
degradation can lead to acidic products, which, in turn, promote corrosion. Plus, hydrolysis
can also materially change the chemical properties of the base fluid, making it unsuitable
for the intended use. Systems that can contract high levels of moisture include systems that
operate at low temperatures or that cycle between high and low temperatures and also
certain fuels such as racing engines running alcohol, which has a cooling effect in the
engine. Racing engines using ester based lubricants should have the lubricant changed
regularly.
Diesters have good lubricating properties, good thermal and shear stability, high viscosity
indexes and have exceptional solvency and detergency. Diesters are superior fluids for
aircraft engines and compressors, although mainly older jet aircraft. Diesters are also used
as a base oil or part of a base oil for automotive engine oils and in some low temperature
greases (note: modern military and commercial jet aircraft almost universally use
lubricants formulated with polyol esters as the base fluid now).
Diesters are incompatible with some sealing materials and can cause more seal swelling
than mineral oils. The scientific reason for this is as follows: diesters have a low
molecular weight that results in low viscosities. This combined with their high polarities
makes them quite aggressive to elastomeric seals. This can be reduced by using better
elastomers or by carefully blending with PAO’s to nullify their swelling effects, since PAO
base stocks are nonpolar.
Esters: Polyolesters (Neopentyl Poly Esters)
Polyol esters are formed by reacting an alcohol with two or more reactive hydroxyl
groups. These fluids are used primarily for aircraft engines, high temperature gas turbines,
hydraulic fluids and heat exchange fluids. Polyol esters are much more expensive than
diesters. Lubricating greases with polyol esters as the base fluid are particularly suited to
high temperature applications. Polyol esters have the same advantages/disadvantages as
diesters. They are, however, much more stable and tend to be used instead of diesters
where temperature stability is important. In general, a polyol ester is thought to be 40-50
deg. C. more thermally stable than a diester of the same viscosity. Esters give much lower
coefficients of friction than those of PAO and mineral oil. By adding 5-10% of an ester to
a PAO or mineral oil the oil’s coefficient of friction can be reduced markedly.
Polymerized alpha olefin: Polyalphaolefin, Olefin Polymers, Olefin Oligomers- a
synthetic hydrocarbon
PAO’s are commonly used to designate olefin oligomers and olefin polymers. The term
PAO was first used by Gulf Oil Company (later acquired by Chevron), but it has now
become an accepted generic term for hydrocarbons manufactured by the catalytic
oligomerization of linear alpha olefins having six or more carbon atoms. PAO’s are
gaining rapid acceptance as high-performance lubricants and functional fluids because they
exhibit certain inherent and highly desirable characteristics. These favorable properties
include:
• A wide operational temperature range.
• Good viscometrics (high viscosity index).
• Thermal Stability.
• Oxidative Stability.
• Hydrolytic stability. *
• Shear stability.
• Low corrosivity.
• Compatibility with mineral oils.
• Compatibility with various materials of construction.
• Low toxicity.
• Manufacturing flexibility that allows “tailoring” products to specific end-use
application requirements.
* Of particular interest in relation to demonstrating superior hydrolytic stability of PAO
fluids is a test that was conducted to find a replacement for a silicate ester based aircraft
coolant/dielectric fluid used by the U.S. military in aircraft radar systems. The test method
required treating the fluids with 0.1% water and maintaining the fluid at 170 or 250 deg. F.
for up to 250 hours. Samples were withdrawn at 20- hour intervals, and the flash points
were measured by the closed cup method. A decrease in flash point was interpreted as
being indicative of hydrolytic breakdown to form lower-molecular-weight products. The
PAO showed no decrease in flash point in any of the test conditions, while the silicate ester
based fluid showed marked decreases. The PAO fluid maintained started out with a flash
point of 300 deg. F. and only dropped to 295 deg. F. at 80 hours into the test, while the
silicate ester fluid, which started out with a flash point of 270 deg. F., ended up with a flash
point of 220 deg. F. at only 55 hours into the test.
PAO’s are used extensively as automotive lubricants (engine, gear, transmission, grease,
hydraulic). PAO’s are also super premium oils for automotive applications operating in
temperature extremes. PAO’s are a synthetic hydrocarbon that is compatible with mineral
oils. In industrial applications, they may be combined with organic esters to be used in
high temperature gear and bearing oils, as well as gas turbines. They are also used as a
base fluid in some wide temperature range greases.
The general manufacturing process used to form PAO’s is performed by combining a low
molecular weight material, usually ethylene gas, into a specific olefin which is
oligomerized into a lubricating oil material and then hydrogen stabilized. There are a
variety of basic building block molecules used to form the finished lubricant, which are
dependent on the range of requirements of the specific lubricant.
Seal compatibility is an important factor for any lubricant. Unlike mineral oils, PAO does
not have a tendency to swell elastomeric materials. Early commercial PAO products were
not formulated properly to allow for this difference in behavior. Consequently, early
PAO’s gained an undeserved reputation for leakage. Extensive tests have since shown that
the addition of small quantities of an ester to the formulation easily alleviates this
problem.
Recent work has indicated that the proper choice of other performance additives may
eliminate the need to employ esters, but this approach is not yet in practice for crankcase
applications. In a test of a PAO vs. a mineral oil for seal compatibility, four seal materials
were studied: acrylate, silicone, nitrile and fluoroelastomer. The seals were evaluated at
the end of the test for changes in tensile strength, elongation, volume (seal swell), and
hardness. The PAO performance fell within the specification limits for all four
elastomers. The mineral oil failed with silicone. Similar tests have been carried out with
fully formulated part- and full-synthetic PAO oils. In all cases the fluids met the
specifications.
Recent data shows that PAO-based fluids provide superior performance for the high-tech
cars and trucks being built today. Today’s engines are smaller and more demanding and
operate at higher RPM’s and under hood spaces is limited which causes increased
operating temperatures. Both the thermal conductivity and heat capacity of PAO fluids are
about 10% higher than values for comparable mineral oils. The net result is that PAOlubricated
equipment tends to run cooler.
Alkylated Aromatics- Dialkylbenzenes- a synthetic hydrocarbon
This synthetic hydrocarbon is compatible with mineral oils and is used as a base oil in
many industrial applications such as engine, gear, hydraulic, air compressor and gas
turbine fluids and in greases for sub-zero applications. These fluids are somewhat toxic
and have poor biodegradability
This lubricant is formed by the alkylation of an aromatic compound, usually benzene.
Alkylated aromatics have excellent low temperature fluidity. Their viscosity indexes are
marginally higher than a high viscosity index mineral oil and they are oxidation resistant
and stable at high temperatures and hydrolytically stable.
Alkylated aromatics were developed for functional fluid use as early as the 1928-1936 time
period but failed to gain any commercial prominence. There was some development and
use of these fluids by the Germans from 1942-1945 due to petroleum oil supply
interruptions cause by the war, but the war ended before they could get production volume
increased to what they required.
It wasn’t until the search for oil in Alaska and Canada in the 1960’s and the construction of
the Alaska pipeline in the 1970’s that the good low temperature properties of alkylated
aromatics became important. Conoco was the major company behind the introduction of
alkylated aromatic base stock lubricants for service during this era.
Phosphate Esters
The major feature of these fluids is their fire resistance. They find extensive use as
hydraulic fluids in aircraft hydraulic systems, underground mining hydraulic systems, high
temperature compressors and steam turbines, where fire resistance is critical. They have
poor compatibility with some sealing materials and most paints. The manufacturing
process of phosphate esters is extremely complex and will not be covered in this book.
Where safety is critical and there are high operating temperatures and/or pressures,
phosphate esters are the lubricant of choice.
Summary
There is clearly no doubt that synthetic lubricants are superior to petroleum based oils. An
excellent summary of in-depth studies that were conducted on the benefits of synthetic
lubricants is presented in Appendix B of the Society for Automotive Engineers, Progress in
Technology Series 22 and was conducted during the 1970’s and 1980’s. The nine superior
performance features of synthetic engine oils that were documented by extensive
laboratory and field testing are listed below:
Nine Superior Performance Features of Synthetic Engine Oils
1. Engine Cleanliness.
2. Improved Fuel Economy (4.2% average increase)
3. Oil Economy (lower consumption)
4. Excellent Cold Starting and Low Temperature Fluidity
5. Outstanding Performance in Extended Oil Drain Field Service
6. High Temperature Oxidation Resistance
7. Outstanding Single and Double Length SAE-ASTM API “SE” and “SF”
Performance Tests (note SE and SF specs were the latest at the time of the testing)
8. Excellent Wear Protection
9. Extended drain capability for heavy-duty diesel trucks and gasoline powered
trucks. Note: this particular test was based on truck fleet testing, however extended
drain capability holds true for passenger cars as well.
These same superior performance features of synthetic engine oils hold true today just as
they did when this extensive testing was conducted and has since been verified by many
more studies and testing as well as countless millions of miles of field service in every
possible type of vehicle and equipment application
ESTERS IN SYNTHETIC LUBRICANTS"
In the simplest terms, esters can be defined as the reaction products of acids and
alcohols. Thousands of different kinds of esters are commercially produced for a broad
range of applications. Within the realm of synthetic lubrication, a relatively small but still
substantial family of esters have been found to be very useful in severe environment
applications. This paper shall provide a general overview of the more common esters used
in synthetic lubricants and discuss their important benefits and utilities.
Esters have been used successfully in lubrication for more than 50 years and are the
preferred stock in many severe applications where their benefits solve problems or bring
value. For example, esters have been used exclusively in jet engine lubricants worldwide
for over 40 years due to their unique combination of low temperature flowability with
clean high temperature operation. Esters are also the preferred stock in the new synthetic
refrigeration lubricants used with CFC replacement refrigerants. Here the combination of
branching and polarity make the esters miscible with the HFC refrigerants and improves
both low and high temperature performance characteristics. In automotive applications, the
first qualified synthetic crankcase motor oils were based entirely on esters and these
products were quite successful when properly formulated. Esters have given way to PAOs
in this application due to PAOs lower cost and their formulating similarities to mineral oil.
Nevertheless, esters are nearly always used in combination with PAOs in full synthetic
motor oils in order to balance the effect on seals, solubilize additives, reduce volatility, and
improve energy efficiency through higher lubricity. The percentage of ester used in motor
oils can vary anywhere from 5 to 25% depending upon the desired properties and the type
of ester employed.
The new frontier for esters is the industrial marketplace where the number of
products, applications, and operating conditions is enormous. In many cases, the very same
equipment which operates satisfactorily on mineral oil in one plant could benefit greatly
from the use of an ester lubricant in another plant where the equipment is operated under
more severe conditions. This is a marketplace where old problems or new challenges can
arise at any time or any location. The high performance properties and custom design
versatility of esters is ideally suited to solve these problems. Ester lubricants have already
captured certain niches in the industrial market such as reciprocating air compressors and
high temperature industrial oven chain lubricants. When one focuses on high temperature
extremes and their telltale signs such as smoking, wear, and deposits, the potential
applications for the problem solving ester lubricants are virtually endless.
Ester Chemistry
In many ways esters are very similar to the more commonly known and used
synthetic hydrocarbons or PAOs. Like PAOs, esters are synthesized from relatively pure
and simple starting materials to produce predetermined molecular structures designed
specifically for high performance lubrication. Both types of synthetic basestocks are
primarily branched hydrocarbons which are thermally and oxidatively stable, have high
viscosity indices, and lack the undesirable and unstable impurities found in conventional
petroleum based oils. The primary structural difference between esters and PAOs is the
presence of multiple ester linkages (COOR) in esters which impart polarity to the
molecules. This polarity affects the way esters behave as lubricants in the following ways:
1. Volatility: The polarity of the ester molecules causes them to be attracted to one
another and this intermolecular attraction requires more energy (heat) for the esters
to transfer from a liquid to a gaseous state. Therefore, at a given molecular weight
or viscosity, the esters will exhibit a lower vapor pressure which translates into a
higher flash point and a lower rate of evaporation for the lubricant. Generally
speaking, the more ester linkages in a specific ester, the higher its flash point and
the lower its volatility.
2. Lubricity: Polarity also causes the ester molecules to be attracted to positively
charged metal surfaces. As a result, the molecules tend to line up on the metal
surface creating a film which requires additional energy (load) to penetrate. The
result is a stronger film which translates into higher lubricity and lower energy
consumption in lubricant applications.
3. Detergency/Dispersency: The polar nature of esters also makes them good
solvents and dispersants. This allows the esters to solubilize or disperse oil
degradation by-products which might otherwise be deposited as varnish or sludge,
and translates into cleaner operation and improved additive solubility in the final
lubricant.
4. Biodegradability: While stable against oxidative and thermal breakdown, the ester
linkage provides a vulnerable site for microbes to begin their work of biodegrading
the ester molecule. This translates into very high biodegradability rates for ester
lubricants and allows more environmentally friendly products to be formulated.
Another important difference between esters and PAOs is the incredible versatility
in the design of ester molecules due to the high number of commercially available acids
and alcohols from which to choose. For example, if one is seeking a 6 cSt (at 100°C)
synthetic basestock, the choices available with PAOs are a "straight cut" 6 cSt product or a
"dumbbell" blend of a lighter and heavier PAO. In either case, the properties of the
resulting basestock are essentially the same. With esters, literally dozens of 6 cSt products
can be designed, each with a different chemical structure selected for the specific desired
property. This allows the "ester engineer" to custom design the structure of the ester
molecules to an optimized set of properties determined by the end customer or defined by
the application. The performance properties that can be varied in ester design include
viscosity, viscosity index, volatility, high temperature coking tendencies, biodegradability,
lubricity, hydrolytic stability, additive solubility, and seal compatibility.
As with any product, there are also drawbacks to esters. The most common concern
when formulating with ester basestocks is compatibility with the elastomer materials used
in the seals. All esters will tend to swell and soften most elastomer seals however, the
degree to which they do so can be controlled through proper selection. When seal swell is
desirable, such as in balancing the seal shrinkage and hardening characteristics of PAOs,
more polar esters should be used such as those with lower molecular weight and/or higher
number of ester linkages. When used as the exclusive basestock, the ester should be
designed for compatibility with seals or the seals should be changed to those types which
are more compatible with esters.
Another potential concern with esters is their ability to react with water or
hydrolyze under certain conditions. Generally this hydrolysis reaction requires the
presence of significant amounts of water and heat with a relatively strong acid or base to
catalyze the reaction. Since esters are usually used in very high temperature applications,
high amounts of water are generally not present and hydrolysis is rarely a problem in
actual use. Where the application environment may lead to hydrolysis, the ester structure
can be designed to greatly improve its hydrolytic stability and additives can be selected to
minimize any effects.
The following is a discussion of the structures and features of the more common
ester families used in synthetic lubrication.
Diesters
Diesters were the original ester structures introduced in synthetic lubricants during the
second World War. These products are made by reacting monohydric alcohols with dibasic
acids creating a molecule which may be linear, branched, or aromatic and with two ester
groups. Diesters, which are often abbreviated DBE (dibasic acid esters), are named after
the type of dibasic acid used and are often abbreviated with letters. For example, a diester
made by reacting octyl alcohol with adipic acid would be known as an "adipate" type
diester and would be abbreviated "DOA" (Dioctyl adipate).
Listed below are the more common dibasic acids used in synthetic lubricants, the family
name for such products, and the alcohols most commonly employed.
DIESTER TYPES AND AVAILABLE ALCOHOLS
Common Acids
No. of
Carbons
Ester
Family
Available
Alcohols
Adipic 6 Adipates
n-octyl
isooctyl
2-Ethylhexyl
isononyl
isodecyl
tridecyl
Azaleic 9 Azelates
Sebacic 10 Sebacates
Dodecanedioic 12 Dodecanedioates
Phthalic 8 Phthalates
Dimer 36 Dimerates
Adipates are the most widely used diesters due to their low relative cost and good
balance of properties. They generally range from about 2.3 to 5.4 cSt at 100°C and exhibit
pour points below -60°C. The viscosity indices of adipates usually run from about 130 to
150 and their oxidative and thermal stability like most of the diesters are comparable to
PAO. The primary difference between adipate diesters and PAOs is the presence of two
ester linkages and the associated benefits outlined previously. The most common use of
adipate diesters is in combination with PAOs in numerous applications such as screw
compressor oils, gear and transmission oils, automotive crankcase oils, and hydraulic
fluids. Adipates are also used as the sole basestock where biodegradability is desired or
high temperature cleanliness is critical such as in environmentally friendly lubricants,
textile lubricants and reciprocating air compressors oils.
Azelates, sebacates, and dodecanedioates are similar to adipates except that in each
case the carbon chain length (backbone) of the dibasic acid is longer. This "backbone
stretching" significantly increases viscosity index and improves the lubricity characteristics
of the ester while retaining all the desirable properties of the adipates. The only downside
to these types of diesters is price which tends to run about 50 - 100% higher than adipates
at the wholesale level. This group of linear DBEs are mainly used in older military
specifications and where the lubricity factor becomes an important parameter.
Phthalates are aromatic diesters and this ring structure greatly reduces the viscosity
index (usually well below 100) and eliminates most of the biodegradability benefit. In all
other respects, phthalates behave similar to other diesters and are about 20 - 30% lower in
cost. Phthalates are used extensively in air compressor lubricants (especially the
reciprocating type) where low viscosity index is the norm and low cost clean operation is
desirable.
Dimer acid is made by combining two oleic acids which creates a large branched
dibasic acid from which interesting diesters are made. Dimerates exhibit high viscosity and
high viscosity indices while retaining excellent low temperature flow. Compared to
adipates, dimerates are higher in price (30 - 40%), have marginal biodegradability, and are
not as clean in high temperature operations. Their lubricity is excellent and they are often
used in synthetic gear oils and 2-cycle oils.
The alcohols used to make diesters will also affect the properties of the finished
esters and thus are important factors in the design process. The alcohols may be reacted
alone or blended with other alcohols to form co-esters with their own unique properties.
The first three alcohols in the table above all contain eight carbons and when reacted with
adipic acid all create a "dioctyl adipate"; however, the properties are entirely different. The
n-octyl adipate would have the highest viscosity and the highest viscosity index (about
50% higher then the 2-ethylhexyl adipate) but would exhibit a relatively high freeze point
making their use in low temperature applications virtually impossible. By branching the
octyl alcohol, the other two DOAs exhibit no freeze point tendencies and have pour points
below -70°C. The isooctyl adipate offers the best balance of properties combining a high
viscosity index with a wide temperature range. The 2-ethylhexyl adipate has a VI about 45
units lower and a somewhat higher volatility. These examples demonstrate the importance
of combining the right alcohols with the right acids when designing diester structures and
allows the ester engineer a great deal of versatility in his work.
Polyol esters
The term "polyol esters" is short for neopentyl polyol esters which are made by reacting
monobasic fatty acids with polyhedric alcohols having a "neopentyl" structure. The unique
feature of the neopentyl structure of polyol alcohols molecules is the fact that there are no
hydrogens on the beta-carbon. Since this "beta-hydrogen" is the first site of thermal attack
on diesters, eliminating this site substantially elevates the thermal stability of polyol esters
and allows them to be used at much higher temperatures. In addition, polyol esters usually
have more ester groups than the diesters and this added polarity further reduces volatility
and enhances the lubricity characteristics while retaining all the other desirable properties
inherent with diesters. This makes polyol esters ideally suited for the higher temperature
applications where the performance of diesters and PAOs begin to fade.
Like diesters, many different acids and alcohols are available for manufacturing polyol
esters and indeed an even greater number of permutations are possible due to the multiple
ester linkages. Unlike diesters, polyol esters (POEs) are named after the alcohol instead of
the acid and the acids are often represented by their carbon chain length. For example, a
polyol ester made by reacting a mixture of nC8 and nC10 fatty acids with
trimethylolpropane would be referred to as a "TMP" ester and represented as TMP C8C10.
The following is a list of the more commonly used raw materials for making polyol esters:
POLYOL ESTERS
AND AVAILABLE ACIDS
Common
Alcohols
# of Ester Groups Family
Available
Acids
Neopentyl Glycol 2 NPG Valeric (nC5)
Isopentanoic (iC5)
Hexanoic (nC6)
Heptanoic (nC7)
Octanoic (nC8)
Isooctanoic (iC8)
2-Ethylhexanoic (2EH)
Pelargonic (nC9)
Isononanoic (iC9)
Decanoic (nC10)
Trimethylolpropane 3 TMP
Pentaerythritol 4 PE
DiPentaerythritol 6 DiPE
Each of the alcohols shown above have no beta-hydrogens and differ primarily in the
number of hydroxyl groups they contain for reaction with the fatty acids. The difference in
ester properties as they relate to the alcohols are primarily those related to molecular
weight such as viscosity, pour point, flash point, and volatility. The versatility in designing
these fluids is mainly related to the selection and mix of the acids esterified onto the
alcohols.
The normal or linear acids all contribute similar performance properties with the physicals
being influenced by their carbon chain length or molecular weight. For example, lighter
acids such as valeric may be desirable for reducing low temperature viscosity on the higher
alcohols, or the same purpose can be achieved by esterifying longer acids onto the shorter
alcohols. While the properties of the normal acids are mainly related to the chain length,
there are some more subtle differences among them which can allow the formulator to vary
such properties as oxidative stability and lubricity.
Branched acids add a new dimension since the length, location, and number of branches all
impact the performance of the final ester. For example, a branch incorporated near the acid
group may help to hinder hydrolysis while multiple branches may be useful for building
viscosity, improving low temperature flow, and enhancing oxidative stability and
cleanliness. The versatility of polyol esters is best understood when one considers that
multiple acids are usually co-esterified with the polyol alcohol allowing the ester engineer
to control multiple properties in a single ester. Indeed single acids are rarely used in polyol
esters because of the enchanced properties that can be obtained through co-esterification.
Polyol esters can extend the high temperature operating range of a lubricant by as much as
50 - 100°C due to their superior stability and low volatility. They are also renowned for
their film strength and increased lubricity which is useful in reducing energy consumption
in many applications. The only downside of polyol esters compared to diesters is their
higher price; they are generally 20 - 70% higher on a wholesale basis.
The major application for polyol esters is jet engine lubricants where they have been used
exclusively for more than 30 years. In this application, the oil is expected to flow at -54°C,
pump readily at -40°C, and withstand sump temperature approaching 200°C with drain
intervals measured in years. Only polyol esters have been found to satisfy this demanding
application and incorporating even small amounts of diesters or PAOs will cause the
lubricant to fail vital specifications.
Polyol esters are also the ester of choice for blending with PAOs in passenger car motor
oils. This change from lower cost diesters to polyols was driven primarily by the need for
reduced fuel consumption and lower volatility in modern specifications. They are used in
2-cycle oils as well for the same reasons plus biodegradability.
In industrial markets polyol esters are used extensively in synthetic refrigeration lubricants
due to their miscibility with non-chlorine refrigerants. They are also widely used in a
variety of very high temperature applications such as industrial oven chains, tenter frames,
stationary turbine engines, high temperature grease, fire resistant transformer coolants, fire
resistant hydraulic fluids, and textile lubricants.
In general, polyol esters represent the highest performance level available for high
temperature applications at a reasonable price. Although they cost more than many other
types of synthetics, the benefits often combine to make this chemistry the most cost
effective in severe environment applications. The primary benefits include extended life,
higher temperature operation, reduced maintenance and downtime, lower energy
consumption, reduced smoke and disposal, and biodegradability.
Other Esters
While diesters and polyol esters represent the most widely used ester families in
synthetic lubrication, two other families are worth mentioning. These are monoesters and
trimellitates. Monoesters are made by reacting monohydric alcohols with monobasic fatty
acids creating a molecule with a single ester linkage and linear or branched alkyl groups.
These products are generally very low in viscosity (usually under 2 cSt at 100°C) and
exhibit extremely low pour points and high VIs. The presence of the ester linkage imparts
polarity which helps to offset the high volatility expected with such small molecules.
Hence, when compared to a hydrocarbon of equal molecular weight, a monoester will have
a significantly higher flash point giving it a broader temperature range in use. Monoesters
are used primarily for extremely cold applications such as in Arctic hydraulic oils and deep
sea drilling. They can also be used in formulating automotive aftermarket additives to
improve cold starting.
Trimellitates are aromatic triesters which are similar to the phthalates described
under diesters but with a third ester linkage. By taking on three alcohols, the trimellitates
are significantly more viscous then the linear adipates or phthalates with viscosities
ranging from about 9 to 20 cSt at 100°C. Like phthalates, trimellitates have a low viscosity
index and poor biodegradability and their price is between adipates and polyols.
Trimellitates are generally used where high viscosity is needed as in gear lubricants, chain
lubricants, and grease.
Summary
Esters are a broad and diverse family of synthetic lubricant basestocks which can
be custom designed to meet specific physical and performance properties. The inherent
polarity of esters improves their performance in lubrication by reducing volatility,
increasing lubricity, providing cleaner operation, and making the products biodegradable.
The wide range of available raw materials allow an ester designer to optimize a product
over numerous variables in order to maximize the performance and value to the client.
They may be used alone in very high temperature applications for optimum performance,
or blended with PAOs or other synthetic basestocks where their complementary properties
improve the balance of the finished lubricant. Esters have been used in synthetic lubricants
for more than 50 years and continue to grow as the drive for efficiency make operating
environments more severe. Because of the complexity involved in the designing, selecting,
and blending of an ester basestock, the choice of the optimum ester should be left to a
qualified ester engineer who can better balance the desired propertie
BIOBASE LUBRICANT
Biodegradable/Biobased Lubricants and Greases Lou A. T. Honary,
University of Northern Iowa
The use of vegetable oils and animal fats for lubrication purposes has been practiced for
many years. With the discovery of petroleum and the availability of inexpensive oils,
alternatives became unattractive and were left by the wayside. Attention was refocused on
vegetable oils during wartime and oil shortage situations. For example, during World War
I and World War II, the use of vegetable oils for fuel, lubricants, greases and energy
transfer increased rapidly. Also, the oil embargo of 1973 brought needed attention to
alternatives for petroleum oils.
Over the past two decades, a renewed interest in vegetable oil-based lubricants has
occurred as environmental interest has increased. In Europe during the 1980s, various
mandates and regulations were placed on petroleum products necessitating the use of
biodegradable lubricants. During the 1990s, many American companies began developing
biodegradable products. A prime example is when the Mobil corporation introduced its
Environmental Awareness Lubricants (EAL) line of hydraulic fluids. The Lubrizol
Corporation also developed considerable quantities of additives and sunflower oil-based
lubricants. However, the lack of regulatory mandates in the United States, as well as the
availability of post-Desert Storm low-cost oil, made biodegradable oils too expensive to
compete.
The next decade will recognize more advances in the use of biodegradable lubes and
greases than in any other time in history. There are at least three major reasons for this
upbeat prediction:
1. Patterning after European farmers, U.S. growers’ associations have begun spending
considerable sums of money on research in nonfood “new uses” areas to reduce crop
surpluses.
2. The federal government has introduced initiatives to promote the use of environmentally
friendly products within federal agencies.
3. There have been advancements in biodegradable lubricants technology and genetic
enhancement to seed oils.
Figure 1 shows a comparison of the oxidative stability of several vegetable oils as tested in
the oxidative stability instrument. Whereas conventional soybean oil shows an oxidative
stability index of seven hours, oil from the genetically enhanced soybean shows 192 hours.
Vegetable Oils
Vegetable oils can and have been used as lubricants in their natural forms. They
have several advantages and disadvantages when considered for industrial and machinery
lubrication. On the positive side, vegetable oils can have excellent lubricity, far superior
than that of mineral oil. Lubricity is so potent that in some applications, such as tractor
transmissions, friction materials need to be added to reduce clutch slippage. Some crude
vegetable oils tested at UNI-ABIL have passed hydraulic pump/wear tests, such as ASTM
D2882 and ASTM D2271, in their natural form.
Vegetable oils also have a very high Viscosity Index (VI); for example, 223 for soybean oil
vs. 90 to 100 for most petroleum oils. Restated, the viscosity of a high VI oil changes less
than that of a low VI oil for a given temperature change. The oil’s viscosity does not
reduce as much when exposed to high temperatures, and does not increase as much as
petroleum oils when exposed to cool temperatures.
Another important property of vegetable oils is their high flash/fire points; 610°F (326°C)
is the flash point of soybean oil compared to a flash point of approximately 392°F (200°C)
for mineral oils.
Most importantly, vegetable oils are biodegradable, in general are less toxic, are renewable
and reduce dependency on imported petroleum oils. Additionally, using lubricants and
greases made of soybean oil helps reduce soybean surpluses and helps stabilize soy prices
for American farmers. For most industrial machinery users these products offer
considerable public relations benefits and goodwill within the agricultural community.
On the negative side, vegetable oils in their natural form lack sufficient oxidative stability
for lubricant use. Low oxidative stability means, if untreated, the oil will oxidize rather
quickly during use, becoming thick and polymerizing to a plastic-like consistency.
Chemical modification of vegetable oils and/or the use of antioxidants can address this
problem, but increase the cost. Chemical modification could involve partial hydrogenation
of the vegetable oil and a shifting of its fatty acids. The challenge with hydrogenation is to
determine at what point the process is to cease. Full hydrogenation of oil can lead to solid
products like margarine. Depending on the needed liquidity and pour point of the oil,
optimum hydrogenation is determined. Recent advances in biotechnology have led to the
development of genetically enhanced oilseeds that are naturally stable and do not require
chemical modification and/or use of antioxidants. A soybean seed developed through
DuPont technology, for example, presents more than 83 percent oleic acid as compared to
only 20 percent oleic acid content in conventional soybean oil. Originally developed for
frying applications, this oil has shown about 30 times more oxidative stability and viscosity
stability in hydraulic pump tests conducted at the UNI-ABIL Research Program. High
oleic varieties of canola oil, rapeseed, sunflower and soybean are now becoming standard
base oils for biodegradable lubricants and greases. The primary advantage of soybean is
that it is U.S.-grown and has a well-established infrastructure to deliver the quality,
quantity and economy for these alternative products.
All conventional, chemically modified or genetically modified oils tested at UNI-ABIL
have shown the same levels of biodegradability. Using tests developed by American
Standard for Testing and Materials (ASTM) and Organization for Economic Cooperation
and Development (OECD), the oil is inoculated with bacteria and is kept under controlled
conditions for 28 days. The percentage of oxygen consumption or CO2 evolution is
monitored to determine the degree of biodegradability. Most vegetable oils tested have
shown to biodegrade over 70 percent within that period as compared to petroleum oils
biodegrading at about 15 to 35 percent. For a test to be considered readily biodegradable,
there must be > 60 percent degradation in 28 days. Similarly, using a variety of tests
involving fish, daphnia and other organisms, the toxicity of the vegetable oils are tested. In
this case, in their pure form, both mineral oil and vegetable oils show little toxicity, but
when additives are included, toxicity increases.
Another negative to vegetable oils is their high pour point (the temperature at which oil
loses fluidity and does not flow). This problem too can be addressed by winterization,
addition of chemical additives (pour point suppressants) and/or blending with other fluids
possessing lower pour points. Various synthetic oils can be used for this purpose. With a
combination of these techniques, UNI-ABIL has developed hydraulic fluids with pour
points of -32.8°F (-36°C) for use in snow blowers used by the Iowa Department of
Transportation. Another experimental hydraulic fluid using genetically enhanced oils
meets military specifications for pour points of -65.2°F (-54°C). While the use of
genetically modified seed oils alleviates the problem of oxidation stability, the cold
temperature properties must be enhanced by the addition of chemical pour point
depressants and/or the addition of other liquids with much lower pour points.
If a high degree of biodegradability is required, then biodegradable synthetic esters are
added to improve cold temperature properties. On the other hand, if the attempt is to
maintain the so-called biobased property, where at least 51 percent is of natural
biomaterials, then a portion of the blend could be light mineral oil with low pour points.
The latter will show a higher degree of toxicity and a lower degree of biodegradability.
Future Trends
U.S. farmers are beginning to move toward specialization of crops, specifically growing
specialty crops for specific end-uses. These specialty crops often bring in higher premiums
and are more profitable than growing the same crops when there is a surplus. The use of
genetic modification will create specialty crops with pharmaceutical and health benefits, as
well as crops suitable for machinery lubricants.
Most importantly, the development of enhanced and naturally more stable oilseeds is
reducing prices of some of these lubricants.
In Europe, environmental mandates have expanded the use of these products. In the United
States, the lack of regulatory mandates and higher prices have hindered the growth in
usage. But long-term liability for the management of and the increasing prices for
petroleum are changing the picture.
The soybean market has the infrastructure to meet quality and quantity requirements for
the lubricants industry. The worldwide supply of soy oil is approximately 6.2 billion
gallons, half of which is produced in the United States. Other vegetable oils must be
imported and are generally much more expensive than soybean oil. Due to its inherent low
stability, soybean oil was not used for lubricants until the UNI-ABIL received funding
from the Soybean Promotion Board to study and develop products. Today, after 10 years of
research, field tests and commercialization activities, economical and superior lubricants
and greases are made with U.S.-grown soybean oil. Many of these products are in use by
federal facilities, state of Iowa-owned equipment, and trucking and railroad firms.
UNI-ABIL has licensed 16 formulated lubricants, greases and base oils made of high oleic
soybeans that have been genetically enhanced for stability. These products meet and
exceed industry requirements, and many do not cost much more than their petroleum
counterparts. If these products can compete in performance and price, their environmental
benefits will make them even more appealing to users
Products currently available from soybean oils include: tractor transmission hydraulic
fluid, industrial hydraulic fluids for process and machinery applications, food-grade
hydraulic fluids and greases, greases for use in automotive, railroad and machinery
applications, chainsaw bar oil, gear lubes, compressor oil, and transformer and
transmission line cooling fluids. Currently, field tests are continuing on two-cycle engine
oils, metalworking fluids and other specialty lubricants.
With the government’s lead-by-example initiative, advocacy by growers associations and
advances in lubricant research and biotechnology of oilseeds, the U.S. market will
progressively see more biobased lubricants. As industrial users learn of and use these
products, vegetable oil-based lubricants, also called biodegradable lubricants or biobased
lubricants, will become an important addition to the existing lubricant industry. Due to
their benefits, they will be become more prevalent in applications where environmental
and safety concerns are high, and they will be less prevalent where petroleum products
offer price and performance beyond those possible by biobased products. Rest assured that
environment-friendly biobased lubricants and greases are here to stay.
TEKNOLOGI ADITIF PELUMAS
Beberapa jenis aditif yang sering dipakai adalah :
Lubricant Additive Types
Detergents (Metallic
Dispersants)
Salicylates, Sulfonates, Phenates, Sulfophenates
Ashless Dispersants N-substituted long-chain alkenyl succinimides
High-molecular-weight esters and polyesters
Amine salts of high-molecular-weight organic acids
Mannich base derived from high-molecular-weight alkylated
phenols
*Copolymers of methacrylic or acrylic acid derivatives
containing polar groups such as amines, amides, imines,
imides, hydroxyl, ether, etc.
*Ethylene-propylene copolymers containing polar groups as
above
Oxidation and
Bearing Corrosion
Inhibitors
Organic phosphites
Metal dithiocarbamates
Sulfurized olefins
Zinc dithiophosphates
Antioxidants Phenolic compounds
Aromatic nitrogen compounds
Phosphosulfurized terpenes
Viscosity Modifiers Polymethacrylates
Ethylene-propylene copolymers (OCP)
Styrene-diene copolymers
Styrene-ester copolymers
Antiwear Additives Organic phosphites
Sulfurized olefins
Zinc dithiophosphates
Alkaline compounds as acid neutralizers
Pour Point
Depressants
Wax alkylated naphthalene
Polymethacrylates
Crosslinked wax alkylated phenols
Vinyl acetate/fumaric-acid-ester copolymers
Vinyl acetate/vinyl-ether copolymers
Styrene-ester copolymers
*Also viscosity modifiers
Detergents
Materials of this type are generally molecules having a large hydrocarbon "tail" and a
polar head group. The tail section, an oleophilic group, serves as a solubilizer in the
base fluid, while the polar group is attracted to contaminants in the lubricant.
Although these compounds are commonly called detergents, their function appears to
be the dispersing of particulate matter rather than cleaning up existing dirt and debris.
Therefore, it is more appropriate to categorize them as dispersants. The molecular
structure and a brief outline of the preparation methods for some representative types
of metallic dispersants are discussed below.
Sulfonates
Sulfonates are the products of the neutralization of a sulfonic acid with a metallic base.
The reaction can be illustrated as:
R-SO3H + MO or MOH ——> R-SO3M + H2O
where MO = divalent metal oxide and MOH = divalent metal hydroxide. R represents
the organic radical that acts as an oil solubilizing group.
The molecular weight of the hydrocarbon must be on the order of 350 or more, and the
presence of the organic radical in the molecule is considered necessary for the oil
solubility of the sulfonate. Commercially available sulfonates are of two types:
petroleum sulfonates and synthetic sulfonates.
Petroleum (or natural) sulfonates are metal salts of sulfonic acids that were formerly
byproducts of the sulfuric acid treatment of oil fractions in the manufacture of white
oils. Currently, with the high demand for detergent oils, sulfonates rather than white
oils have become the principal product. The structure of the organic portion of
petroleum sulfonates is not completely known. Depending on the crude oil source, the
structure can have varying proportions of aliphatic, naphthenic, and aromatic
hydrocarbon groups.
Synthetic sulfonates are metal salts of acids produced from the sulfonation of
alkylated aromatics by reaction with sulfur trioxide. In many cases, synthetic sulfonates
were derivatives of benzene with long alkyl substituents, whose structure is illustrated
at left, where R and R' are aliphatic radicals with a combined carbon number over C20.
Most metallic cations of sulfonate detergents are calcium, magnesium, and sodium.
Alkaline-earth sulfonates can be prepared by direct reaction of sulfonic acid with the
metal oxide or hydroxide, or by reacting the sodium sulfonate with the metal chloride.
Oil-soluble sulfonates containing metal in excess of the stoichiometric amount are
called basic sulfonates. Among the advantages of basic sulfonates is a greater ability to
neutralize acidic bodies in addition to serving as a dispersant for contaminants.
Salicylates
Salicylates are generally prepared from alkyl phenols by a chemical scheme known as
the Kolbe reaction.
The potassium salicylate may be metathesized with calcium chloride or magnesium
chloride. The resulting salts are then overbased to form highly basic detergents that
have proven effective in diesel engine oil formulations.
Phenates and Phenol Sulfide Salts
The broad class of metal phenates includes the salts of alkylphenols, alkylphenol
sulfides, and alkylphenol aldehyde products. Oil solubility is provided by alkylating the
phenol with olefins that generally contain seven or more carbon atoms.
Sulfur is incorporated into the phenates by reacting the alkylphenol with sulfur chloride
or elemental sulfur. The introduction of sulfur and the presence of a methylene bridge
lowers the corrosivity of the products toward bearing materials and improves their
antioxidant characteristics.
Calcium phenates are currently the most widely used types. They are manufactured by
reacting the substituted phenols with the oxides or hydroxides of the metals. Basic
phenates can be produced by using an excess of the metal base over the theoretical
amounts required to form neutral phenates. Basic phenates have greater acid
neutralization potential per unit of weight. Such products have two to three times the
amount of metal required for neutral phenates.
In the structures for the various phenates shown, M = divalent metal and R = alkyl
group.
Thiophosphonates
Commercial products of this type are generally derived from acidic components
produced by the reaction between polybutene (500 to 1000 molecular weight range)
and phosphorus pentasulfide. A study of the structure of these compounds indicated
that the organic salts present are principally thiopyrophosphonates, accompanied in
some cases by 10 to 25 mole per cent of thiophosphonates and phosphonates. Oilsoluble
phosphonates and thiophosphonates that contain metal in excess of the
stoichiometric amount can also be prepared. However, these materials have almost
vanished from use.
Dispersants
A major development in the additive field was the discovery and use of ashless dispersants.
These materials may be categorized into two broad types: high-molecular weight
polymeric dispersants used to formulate multigrade oils and lower molecular weight
additives for use where viscosity modification is not necessary. These additives are much
more effective than the metallic types in controlling sludge and varnish deposits that result
from intermittent and low-temperature gasoline engine operation.
Compounds useful for this purpose are again characterized by a polar group attached to a
relatively high molecular weight hydrocarbon chain. The polar group generally contains
one or more of the elements nitrogen, oxygen and phosphorus. The solubilizing chains are
generally higher in molecular weight than those in detergents; however, they may be quite
similar in some instances.
No attempt will be made to describe all the materials that fit into this category. The
discussion will be limited to some of the more widely used commercial products.
N-Substituted Long-Chain Alkenyl Succinimides
The majority of products currently in use are of this type or related materials that
correspond to the following general formula:
The alkenylsuccinic acid intermediate is obtained by condensing an olefin polymer,
generally a polyisobutylene with a molecular weight in the range of 800 to 1200, with
maleic anhydride. The basic part of the additive usually results from N-amino
alkylpolyamines, especially the polyalkylene amines such as triethylenetetramine,
tetraethylene pentamine, etc.
High Molecular Weight Esters
Materials of commercial interest in this area include products formed by the esterification
of olefin substituted succinic acids with mono or polyhydric aliphatic alcohols. The olefin
substituent in the acids has at least 50 aliphatic carbon atoms and a molecular weight of
about 700 to 5000. An example of such a material is the reaction product of ethylene
glycol with a substituted succinic anhydride:
Polyhydric alcohols such as glycerol, pentaerythritol and sorbitol may be employed in such
a reaction.
Mannich Bases from High Molecular Weight Alkylated Phenols
Such products are formed by the condensation of a high molecular weight alkyl-substituted
phenol, an alkylenepolyamine, and an aldehyde such as formaldehyde. A description of the
reaction product from polypropylenephenol, tetraethylenepentamine, and formaldehyde is:
Polymeric Dispersants
These ashless dispersants may serve the dual function of dispersant and viscosity modifier.
They have two different structural features: those that are similar to materials employed as
viscosity modifiers and those of polar compounds (which impart dispersancy). The
viscosity modifiers will be discussed in a separate section. The general formula for
dispersant polymers might be:
where the hydrocarbon portion is the oleophilic group, A = polar group, and R = hydrogen
C1-6 alkyl, C4-6 alkenyl, or alkyl. Some of the many possibilities for the polar groups are:
Oxidation and Bearing Corrosion Inhibitors
The function of an oxidation inhibitor is to prevent deterioration of the lubricant associated
with oxygen attack. These inhibitors either destroy free radicals (chain breaking) or
interact with peroxides involved in the oxidation mechanism. Among the widely used
antioxidants are phenolic types and zinc dithiophosphates. The former are considered to be
of the chain-breaking variety, whereas the latter are believed to be peroxide destroyers.
The corrosion of bearing metal is generally considered to be due largely to reaction of the
acid with the oxides of the bearing metal. In engine operation, these acids either originate
from products of incomplete fuel combustion that find their way into the lubricant as
blowby gases or are produced from lubricant oxidation. Oxidation inhibitors can
significantly reduce this tendency.
Detergents can reduce bearing corrosion by neutralizing the corrosive acids. Other
inhibitors such as zinc dithiophosphates and phosphosulfurized olefins not only inhibit
oxidation but also form a protective film on the bearing surface, making it impervious to
acid attack.
Phenolic Inhibitors (Chain-Breaking)
The inhibitor efficiency of phenol is markedly increased by substituting alkyl groups in the
two ortho and para positions. It is particularly enhanced when the ortho substituents are
bulky groups such as tert-butyl and the para substituent is a primarily alkyl group. A
variety of hindered phenols are produced commercially and employed as inhibitors in
transformer, turbine, and engine oils.
The methylenebis structure is more effective in high-temperature applications due to its
lower volatility characteristics compared to the other molecule.
Zinc Dithiophosphates (Peroxide Destroying)
Of greatest commercial importance in engine lubricants are the zinc dithiophosphates,
which not only serve as antioxidants but also provide both antiwear and bearing corrosion
protection. The zinc dithiophosphates are made as follows:
where R = alkyl or aryl. Both alkyl and aryl derivatives are employed commercially. Alkyl
derivatives are generally more effective as antiwear additives. Aryl derivatives have a
higher degree of thermal stability.
Both the antiwear and thermal stability characteristics of the alkyl compounds can be
varied by using different alcohols; i.e. primary vs. secondary and high vs. low molecular
weight. The principal alkyls are propyl, butyl, hexyl, octyl, and mixtures of these. The
effect of the alkyl radical on the thermal decomposition temperature of zinc
dialkyldithiophosphates (ZDP) is shown below:
Effect of Alkyl Radical on Thermal Decomposition of ZDP
Alkyl Radical Decomposition Temperature (°C)
Isopropyl 196
4-Methyl 2-pentyl 197
N-Amyl 212
N-Octyl >251
Stability increases with the length of the alkyl chain and is lower for secondary alkyl
groups with the same number of carbon atoms. It should be noted, however, that the
overall performance characteristics of ZDPs are not related to the decomposition
temperature.
Antiwear Additives
Wear is the loss of metal with subsequent change in clearance between surfaces moving
relative to each other. If continued, it will result in equipment malfunction. Among the
principal factors causing wear are metal-to-metal contact, presence of abrasive particulate
matter, and attack of corrosive acids.
Metal-to-metal contact can be prevented by adding film-forming compounds that protect
the surface either by physical absorption or chemical reaction. The zinc dithiophosphates
are widely used for this purpose and are particularly effective in reducing wear in
valvetrain mechanisms. These compounds are described under oxidation and bearing
corrosion inhibitors. Other effective additives contain phosphorus, sulfur, or combinations
of these elements.
Abrasive wear can be prevented by effective removal of particulate matter by filtration of
both the air entering the engine and the lubricant during engine operation.
Corrosive wear is largely the result of acidic blowby products formed during fuel
combustion. This type of wear can be controlled by using alkaline additives such as basic
phenates and sulfonates.
Viscosity Modifiers
Viscosity modifiers, or viscosity index improvers as they were formerly known, comprise a
class of materials that improves the viscosity/temperature characteristics of the lubricant.
This modification of rheological properties results in increased viscosity at all
temperatures. The viscosity increase is more pronounced at high temperatures which
significantly improves the viscosity index of the lubricant. This is manifested by a decrease
in the slope of the viscosity/temperature line plotted on ASTM log paper.
Viscosity modifiers are generally oil-soluble organic polymers with molecular weights
ranging from about 10,000 to 1 million. The polymer molecule in solution is swollen by
the lubricant, and the volume of the swollen entity determines the degree to which the
polymer increases viscosity. The higher the temperature, the larger the volume and the
greater the "thickening" effect of the polymer. Hence, the oil tends to "thin" less due to
increased temperature.
In addition to viscosity improvement, the performance of these polymers also depends on
shear stability or resistance to mechanical shear and on their chemical and thermal
stability. With a given polymer system, shear stability decreases with an increase in
molecular weight. The loss due to shear is reflected in a loss in lubricant viscosity. On the
other hand, the "thickening power" of the viscosity modifier increases with an increase in
molecular weight for a given polymer type. A performance balance must then be
established which takes into consideration shear stability and viscosity needs as well as
thermal and oxidative stability in actual engine operation.
Pour Point Depressants
Pour point depressants prevent the congelation of oil at low temperature. This phenomenon
is associated with crystallization of the paraffin wax that is present in mineral oil fractions.
To provide low pour points, the refiner removes wax constituents, which solidify at
relatively high temperatures, in a process known as dewaxing. Complete dewaxing would
reduce the yield of lube oil to an uneconomical level. Therefore, the dewaxing process is
supplemented by using additives that lower the pour point of the oil.
Pour point depressants do not prevent wax from crystallizing in the oil. Rather, they are
absorbed on the wax crystals and, thus, reduce the amount of oil occluded on the crystal.
Reducing the crystal volume permits lubricant flow.
Miscellaneous Additives
This category includes antirust compounds and foam inhibitors. Chemicals employed as
rust inhibitors include sulfonates, alkenyl succinic acids, substituted imidazolines, amines,
and amine phosphates. A considerable amount of information on these additives is
contained in patent literature. Antifoam agents include silicones and miscellaneous organic
copolymers.
4. LUBRICANT FORMULATION
The basic functions of a lubricant are friction and wear reduction, heat removal and
contaminant suspension. Apart from important application in internal combustion engines,
vehicles and industrial gear boxes, compressors, turbines or hydraulic systems, there are
vast number of other applications, which mostly require specifically tailored lubricants.
Designing a lubricant to perform above stated functions in different systems, is a complex
task, involving a careful balance of properties both in the lube base stocks and the
performance enhancing additives. Between 5000 and 10000 different lubricant
formulations are necessary to satisfy more than 90% of all lubricant applications.
Lubricants today are classified into two major groups : Automotive lubricants and
Industrial lubricants. Automotive lubricants have to perform in different types of
vehicles both petrol and diesel under a variety of operating conditions. Modern vehicles are
fuel efficient and comfortable with high levels of performance. They are required to meet
stringent emission norms. Quality requirement of such lubricants are established by the
Society of Automotive Engineers (SAE) and are specified in its classification system.
Industrial lubricants can be subdivided into industrial oils and industrial specialities.
Specialities in this case are principally greases, metal working lubricants and solid
lubricant films. Quality requirements for these types of lubricants are defined by Original
Equipment Manufacturers (OEM) and end users of the products. On the global lubricants
market, automotive lubricants account for more than 60% of volumes sold.
Most lubricants consist of a basestock and various additives selected to improve or
supplement the basestock's performance. The basestock is the primary component, usually 70 to
99% of the finished oil or grease, and its properties play a vital role. To a great degree the
structure and stability of the basestock dictate the flow characteristics of the oil and the
temperature range in which it can operate, as well as many other vital properties such as volatility,
lubricity, and cleanliness. Additives enhance these properties or impart new ones, such as
improving stability at both high and low temperatures, modifying the flow properties, and reducing
wear, friction, rust and corrosion. The basestocks and additives work together and must be
carefully selected and balanced to allow the finished oil to do its intended job, which includes
protecting moving parts from wear, removing heat and dirt, preventing rust and corrosion, and
improving energy efficiency. Since the basestock is the dominate component with the most
important role, one obvious way to make a better oil is to start with a better basestock. That is
exactly what synthetic oils endeavor to accomplish.
The Additives
As mentioned earlier, almost all commercial lubricants contain additives to enhance their
performance. Their amount varies from > 1% to 25% or more. By for the largest market for
additives is in the transportation field, including additives for engines and drive trains in
cars, trucks, buses, locomotive and ships. The function of additives can be summarized as
follows :
· Protect metal surfaces (rings, bearings, gears etc.)
· Extend the range of lubricant applicability
· Extend lubricants' life
The same general range of additive types find application in industrial lubricants as well
along with other materials designed to impart specific properties.
Present day additives consist of a variety of classes. For the automotive lubricants these are
:a) Surface protective additives : antiwear and EP agent, detergent, dispersant and friction
modifiers.
b) Performance additives : Pour point depressant, viscosity modifiers and seal swell agents.
c) Protective additives : antifoament, antioxidant and metal deactivators
Additive - Additive interactions have been widely studied and their performance attributed
to a specific chemistry or functionalities of these interactive additive pairs. Many factors
that govern their applications are : additive must be capable of being handled in
conventional blending equipment, stable in storage, free of offensive odour and non-toxic
by normal industrial standards.
Formulation, Specifications and Testing
The lubricant that one buys in the market and uses in his vehicle, engine and or
machine is normally a formulated product comprising of base stock(s), performance
enhancing additives, and other special ingredients. All the above components when put
together in an appropriate concentration ensures that the formulated / finished lubricant
perform the required functions and meet equipment needs, in which it is being used.
The physico-chemical and performance requirements define a lubricant identity and
its ability to reduce friction, resist oxidation, minimize deposit formation, prevent
corrosion and wear. These requirements may be set at national, regional or global levels by
engine manufacturers public organizations or military authorities. The most widely known
systems for automotive lubricants (being the major category) are API classification and the
European system ACEA (Association Des Constructeurs European d' Automobiles). API
system, which is, commonly use throughout the world relies on cooperation between three
bodies namely : SAE, API and American Society for Testing and Materials (ASTM), each
with a well defined role and responsibility.
API performance classification system, introduced in 1970, gave the gasoline
engine, the prefix 'S' (for service station) followed by a series of letter from 'A' onward
indicating successive level of increased quality or upgrading which currently stands at 'SJ',
introduced in 1996. Similar to the above system, diesel engine oils are coded using a prefix
'C' (for commercial) which now stands at CH-4 or higher introduced in 1998 for the 4-
stroke engine.
As with 4-stroke engine oils, there exist a similar system for two-stroke engine oils
as well. Two stroke oils are allocated to certain performance groups, which provide
information about suitable applications. API service groups, Japanese Automotive
Standard Organization (JASO) Classification and the International Standards Organization
(ISO) classification system are currently followed in most of the world.
Lubricant effectiveness is assessed by bench scale and full scale testing in the
laboratory and in the field. The laboratory tests are accelerated test in real-world equipment
that simulates actual service conditions. These tests are actual engines, transmissions,
axles, hydraulic pumps and so on and are run under standard conditions according to the
prescribed procedures. The tests are complex and expensive. The goal here is to ascertain
the lubricants meet the performance requirements established by the various organizations,
which appear in delivery conditions, in house standard and general specifications.
Lubricating greases which also form part of the lubricants industry as a whole are by
definition solid to semi solid fluid products created by the dispersion of a thickening agent
in a liquid lubricant, usually a metal soap along with certain additive compounds which
impart special properties, processed in a grease plant to produce a gel like material. By far
the most important application of greases is for the lubrication of rolling element bearings.
Greases continued to be classified by the procedure defined by National Lubricating
Grease Institute (NLG) USA in accordance with cone penetration method.
4.1 ENGINE OILS
Introduction
The automobile industry is the major user of lubricants. Engine designs have been
continually improved to reduce weight, increase fuel economy, increase power output, and
at the same time meet environmental emission guidelines. Research is ongoing to
formulate lubricants to meet the demands of the redesigned engines. In general, a lubricant
must perform nine functions for the efficient operation of the engine.
#1. Permit Easy Starting
An engine oil must be thin enough when first starting the engine to allow for sufficient
cranking speed. The oil must then be able to flow immediately to lubricate vital engine
components. Most of the engine wear occurs at start-up before the oil can reach all the
engine parts. As the engine is heated, the oil must not become too thin and be unable to
provide adequate engine lubrication. The viscosity of the oil is the measure of this
resistance to flow.
The effect of temperature on viscosity varies widely with different types of oil. The
standard used to measure the amount of viscosity change with temperature is the Viscosity
Index (V.I). An oil with a high viscosity index shows less change in viscosity over a wider
temperature range. Refer to the Glossary of Terms, and the Additive section of this site for
more information. A "multi-grade" oil has a high viscosity index.
Synthetic oils have the best low temperature flow characteristics, and are worth the extra
cost in northern climates during the winter months.
#2. Lubricate and Prevent Wear
The engine is now started, and the oil is being circulated by the oil pump to the engine
parts. The oil must now prevent the metal-to-metal contact that will result in wear to the
moving parts.
Full-film lubrication occurs when the moving surfaces are continuously separated by a film
of oil. The viscosity of the oil must remain high enough to prevent metal-to-metal contact.
Wear will only occur if the surface is scratched by particles thicker then the oil film.
Crankshaft bearings, connecting rods, camshaft, and piston pins normally operate with fullfilm
lubrication.
In some conditions, it is impossible to maintain a continuous oil film between the moving
parts. Intermittent metal-to-metal contact occurs because of high spots on sliding surfaces,
during engine starting, and in new or rebuilt engines. Lubrication under these conditions is
referred to as boundary lubrication. This lubrication is accomplished by the additive
package in the oil. Refer to the Glossary of Terms for further information on boundary
lubrication.
#3. Reduce Friction
Under full-film lubrication conditions, the film of oil prevents metal-to-metal contact. The
viscosity of the oil should be high enough to maintain the film. A delicate balance must be
maintained. If the viscosity is higher then required, the engine must overcome the excess
fluid friction.
It is important to note that the viscosity of the oil changes as it becomes contaminated.
Dirt, oxidation and sludge will increase the viscosity of the oil while fuel dilution will
reduce the viscosity. This is the reason why the oil must be changed as per the schedule in
the owners manual.
#4. Protect Against Rust and Corrosion
Under perfect conditions, fuel burns to form carbon dioxide and water. For each gallon of
fuel burned, a gallon or more of water is produced. Most of this water should escape as a
vapor out of the exhaust, but some does condense on the cylinder walls. Also, water passes
by the piston rings and becomes trapped in the crankcase. This is more of a problem in
cold weather before the engine is warm.
In addition to water, other corrosive combustion gases also get past the rings, and are
dissolved in the crankcase oil. Add to this the acids formed by the normal oxidation of oil,
and the potential for rust and corrosive engine deposits become significant.
Corrosion inhibitors are part of the additive package to protect non-ferrous metals by
coating them, and forming a barrier between the parts and the acids. Also, rust inhibitors
are added to the oil to protect iron/steel surfaces from oxygen attack by forming a
protective screen.
#5. Keep Engine Parts Clean
For a variety of reasons, a gasoline or diesel engine does not burn all the fuel completely.
Some of the partially burned gasoline or diesel fuel undergoes complex chemical changes
during combustion, and under some conditions forms soot or carbon. Most of the partially
burned fuel escapes in the form of soot through the exhaust, but part escapes past the rings
into the crankcase. This combines with water to form sludge, and varnish deposits on
engine parts. Sludge buildup may clog oil passages which reduces oil flow. Varnish
buildup interferes with the proper clearances, restricts oil circulation, and causes vital
engine parts to stick and malfunction.
Straight mineral oils have a very limited ability to keep these contaminants from forming
sludge within the engine. Detergents are part of the additive package to clean-up existing
deposits in the engine, as well as disperse insoluble matter into the oil. Dispersants are also
part of the additive package. Both detergents and dispersants attach themselves to
contaminated particles and hold them in suspension. The suspended particles are so finely
divided that they can pass harmlessly between the mating surfaces, and through the oil
filter. This contamination is removed when the oil is changed. Another good reason for
your scheduled oil change!
#6. Minimize Combustion Chamber Deposits
Some oil must reach the area of the top of the piston ring in order to lubricate the rings and
the cylinder walls. It is important that the oil prevent excessive combustion deposits.
Combustion deposits act as a heat barrier and as a result pistons, rings, spark plugs, and
valves are not properly cooled. We all know about carbon fouled spark plugs.
The motor oil must accomplish two things in preventing excessive combustion deposits:
1. The oil must keep the rings free so as to reduce the amount of oil reaching the
combustion chamber.
2. The portion of the oil reaching the combustion chamber must burn as clean as
possible.
#7. Cool Engine Parts
The cooling system performs about 60% of the cooling job of the engine. It cools the upper
part of the engine including the cylinder heads, cylinder walls, and valves. The crankshaft,
the main and connecting rod bearings, the timing gears, the pistons and other components
in the lower engine are cooled as the oil flows around the parts.
What is critical is the continuous circulation of large quantities of oil. If oil passages are
allowed to become clogged, the flow is restricted, and the parts are not cooled properly.
Another good reason to change your oil on a regular basis, and check the oil level!
#8. Seal Combustion Pressures
The surfaces of the piston rings, ring grooves, and cylinder walls are not completely
smooth. This would become evident under a microscope as small hills and valleys. For this
reason, the rings can never prevent high combustion and compression pressures from
escaping into the low pressure area of the crankcase. This would result in a reduction of
engine power and efficiency. Motor oil fills in the hills and valleys and greatly improves
the seal. Because the oil film is only about 0.025 mm thick, it cannot compensate for
excessive wear of the rings, ring grooves, or cylinder walls. In a new or rebuilt engine, oil
consumption will be relatively high until these surfaces have been smoothed out enough to
allow the oil to form a good seal.
#9. Engine Oil Must be Non-Foaming
Because of the rapidly moving parts in an engine, oil is constantly being mixed with air.
This produces foam which is a lot of air bubbles which may or may not readily collapse.
These air bubbles normally rise to the surface and break, but water and other contaminants
slow this process.
Foam is not a good conductor of heat, and will impair the cooling of the engine parts. Also,
foam does not have the ability to carry much of a load which would result in excessive
engine wear.
Foam depressant additives are used in the manufacture of automotive lubricants, to reduce
the amount of foaming.
Physical Requirements For Engine Oils
SAE has established that twelve viscosity grades are suitable for engine lubricating oils.
The physical requirements for these viscosity grades are described in SAE J300, which is
intended for use by engine manufacturers in determining engine oil viscosity grades
suitable for use in their engines.
The Fuels and Lubricants Activity of SAE recently approved changes to the Cold Cranking
Simulator (CCS) limits for multigrade engine oils as defined in SAE J300. The changes
entail measuring viscosity at 5°C lower temperature and imposing higher maximum
viscosity limits for all W-grades. The standard was modified based upon data
demonstrating that modern passenger car engines start at lower temperatures and with
higher viscosity oils than engines that were used to establish the previous CCS limits.
The new standard carries a revision date of December 1999. Mandatory compliance with
the new CCS limits begins June 2001. Until then, either the old April 1997 or the new
December 1999 CCS limits may be used to demonstrate compliance.
The new CCS viscosity maximums are roughly double the old limits. The new limits for
0W and 5W oils are increased by less than a factor of two because engine oils formulated
with API Group I and II base oils have been shown to roughly double in CCS viscosity for
every 5°C reduction in temperature. Those containing higher VI oils, such as API Group
III and IV, increase viscosity by a factor of ~1.7 for every 5°C drop in temperature. Both
fuel economy and volatility specifications in the proposed ILSAC GF-3 performance
category are expected to increase the use of API Group III and IV base oils, especially in
0W, 5W and 10W oils. Furthermore, many oil marketers expect to offer products with
CCS viscosities near the lower implicit limit to pass the Sequence VIB fuel economy test.
The new CCS limits for 0W and 5W oils were chosen to reduce the likelihood that ILSAC
GF-3 lubricants would drop a grade due solely to changes in SAE J300. For example, a
synthetic SAE 5W-30 passenger car engine oil has a CCS viscosity of 2200 cP at -25°C,
3750 cP at -30°C and 6380 cP at -35°C. This fluid is classified as an SAE 5W oil by both
the old and new CCS limits. If, however, the 0W maximum CCS viscosity were 6500 cP
(i.e., double the old limit of 3250 cP), this synthetic lubricant would have to be reclassified
as an SAE 0W oil.
Current and future low and high temperature viscosity requirements for these viscosity
grades are shown below. In additon, the U.S. military imposes additional requirements on
oils it purchases.
SAE Viscosity Grades for Engine Oilsa — SAE J300 Apr 97
SAE
Viscosity
Grade
Low Temperature Viscosities High-Temperature Viscosities
Crankingb (cP)
max at temp °C
Pumpingc (cP) max with
no yield stress at temp °C
Low Shear Rate
Kinematicd (cSt) at
100°C
High Sheare Rate (cP) at 150°C
min
min max
0W 3250 at -30 60,000 at -40 3.8 — —
5W 3500 at -25 60,000 at -35 3.8 — —
10W 3500 at -20 60,000 at -30 4.1 — —
15W 3500 at -15 60,000 at -25 5.6 — —
20W 4500 at -10 60,000 at -20 5.6 — —
25W 6000 at -5 60,000 at -15 9.3 — —
20 — — 5.6 <9.3 2.6
30 — — 9.3 <12.5 2.9
40 — — 12.5 <16.3
2.9 (0W-40, 5W-40, 10W-40
grades)
40 — — 12.5 <16.3
3.7 (15W-40, 20W-40, 25W-
40, 40 grades)
50 — — 16.3 <21.9 3.7
60 — — 21.9 <26.1 3.7
a All values are critical specifications as defined by ASTM D 3244 (see text, Section 3).
b ASTM D 5293
c ASTM D 4684 (see also Appendix B and text Section 4.1): The presence of any yield
stress detectable by this method constitutes a failure regardless of viscosity.
d ASTM D 445
e ASTM D 4683, ASTM D 4741, CEC-L-36-A-90
SAE Viscosity Grades for Engine Oilsa — SAE J300 Dec 99
SAE
Viscosity
Grade
Low Temperature Viscosities High-Temperature Viscosities
Crankingb (cP)
max at temp °C
Pumpingc (cP) max
with no yield stress at
temp °C
Low Shear Rate
Kinematicd (cSt) at
100°C High Sheare Rate (cP) at 150°C min
min max
0W 6200 at -35 60,000 at -40 3.8 — —
5W 6600 at -30 60,000 at -35 3.8 — —
10W 7000 at -25 60,000 at -30 4.1 — —
15W 7000 at -20 60,000 at -25 5.6 — —
20W 9500 at -15 60,000 at -20 5.6 — —
25W 13,000 at -10 60,000 at -15 9.3 — —
20 — — 5.6 <9.3 2.6
30 — — 9.3 <12.5 2.9
40 — — 12.5 <16.3 2.9 (0W-40, 5W-40, 10W-40 grades)
40 — — 12.5 <16.3
3.7 (15W-40, 20W-40, 25W-40, 40
grades)
50 — — 16.3 <21.9 3.7
60 — — 21.9 <26.1 3.7
a All values are critical specifications as defined by ASTM D 3244 (see text, Section 3).
b ASTM D 5293
c ASTM D 4684 (see also Appendix B and text Section 4.1): The presence of any yield
stress detectable by this method constitutes a failure regardless of viscosity.
d ASTM D 445
e ASTM D 4683, ASTM D 4741, CEC-L-36-A-90
Military Grades
Specification: MIL-PRFCID
2104G 2104G 2104G
A-A-52039B
A-A-52039B
2104G
A-A-52306A
Viscosity Grade 10W 30 40 5W-30 10W-30 15W-40
Cranking Viscositya (cP) at temperature °C
min
max
3500 at -25
3500 at -20
—
—
—
—
3500 at -30
3500 at -25
3500 at -25
3500 at -20
3500 at -20
3500 at -15
Pumping Viscosityb (cP) at temp °C, max 30,000 at -25 — — 30,000 at -30 30,000 at -25 30,000 at -20
Viscosityc (cSt) at 100°C
min
max
5.6
<7.4
9.3
<12.5
12.5
<16.3
9.3
<12.5
9.3
<12.5
12.5
<16.3
Viscosity Index, min — 80 80 — — —
HTHS Viscosity (cP) min 2.9 — — 2.9 2.9 3.7
Pour Point (°C) max -30 -18 -15 -35 -30 -23
Stable Pour Point (°C) max -30 — — -35 -30 -23
Flash Point (°C) min 205 220 225 200 205 215
Evaporative Lossd
(%) max
18 — — 20 17 15
a ASTM D 2602 Modified
b ASTM D 4684, allows no detectable yield stress
c ASTM D 445
d Not required for all military specifications
Engine Oil Classification System For Automotive Gasoline Engine
Service
"S" — SERVICE OILS
API Automotive
Gasoline Engine
Service Categories
Previous API
Engine Service
Categories
Related
Industry
Definitions
Engine Test Requirements
SA ML
Straight mineral
oil
None
SB MM Inhibited oil only CRC L-4* or L-38; Sequence IV*
SC MS (1964) 1964 Models
CRC L-38; Sequence IIA*; Sequence IIIA*; Sequence IV*;
Sequence V*; Caterpillar L-1* (1% sulfur fuel)
SD MS (1968) 1968 Models
CRC L-38; Sequence IIB*; Sequence IIIB*; Sequence IV*;
Sequence VB*; Falcon Rust*; Caterpillar L-1* or 1H*
SE None 1972 Models
CRC L-38; Sequence IIB*; Sequence IIIC* or IIID*; Sequence
VC* or VD*
SF None 1980 Models CRC L-38; Sequence IID; Sequence IIID*; Sequence VD*
SG None 1989 Models
CRC L-38; Sequence IID; Sequence IIIE; Sequence VE;
Caterpillar 1H2*
SH None 1994 Models CRC L-38; Sequence IID; Sequence IIIE; Sequence VE
SJ None 1997 Models CRC L-38; Sequence IID; Sequence IIIE; Sequence VE
* This test is obsolete; engine parts, test fuel, or reference oils are no longer generally available, or the test is
no longer monitored by the test developer or ASTM.
SA — Formerly for Utility Gasoline and Diesel Engine Service (Obsolete) — Category
SA denotes service typical of older engines operated under such mild conditions that the
protection afforded by compounded oils is not required. This category has no performance
requirements, and oils in this category should not be used in any engine unless specifically
recommended by the equipment manufacturer.
SB — Minimum-Duty Gasoline Engine Service (Obsolete) — Category SB denotes
service typical of older engines operated under such mild conditions that only minimum
protection afforded by compounding is desired. Oils designed for this service have been
used since the 1930s and provide mild antiscuff capability and resistance to oil oxidation
and bearing corrosion. They should not be used in any engine unless specifically
recommended by the equipment manufacturer.
SC — 1964 Gasoline Engine Service (Obsolete) — Category SC denotes service typical
of gasoline engines in 1964 through 1967 models of passenger cars and some trucks,
operating under engine manufacturers' warranties in effect during those model years. Oils
designed for this service provide control of high and low-temperature deposits, wear, rust,
and corrosion in gasoline engines.
SD — 1968 Gasoline Engine Service (Obsolete) — Category SD denotes service typical
of gasoline engines in 1968 through 1970 models of passenger cars and some trucks,
operating under engine manufacturers' warranties in effect during those model years. This
category may also apply to certain 1971 or later models as specified (or recommended) in
the ownersí manuals. Oils designed for this service provide more protection against high
and low-temperature deposits, wear, rust, and corrosion in gasoline engines than oils that
are satisfactory for API Engine Service Category SC and may be used when API Engine
Service Category SC is recommended.
SE — 1972 Gasoline Engine Service (Obsolete) — Category SE denotes service typical
of gasoline engines in passenger cars and some trucks beginning with 1972 and certain
1971 through 1979 models operating under engine manufacturers' warranties. Oils
designed for this service provide more protection against oil oxidation, high-temperature
engine deposits, rust, and corrosion in gasoline engines than oils that are satisfactory for
API Engine Service Categories SD or SC and may be used when either of these categories
is recommended.
SF — 1980 Gasoline Engine Service (Obsolete) — Category SF denotes service typical
of gasoline engines in passenger cars and some trucks beginning with 1980 through 1989
models operating under engine manufacturers' recommended maintenance procedures. Oils
developed for this service provide increased oxidation stability and improved antiwear
performance relative to oils that meet the minimum requirements of API Service Category
SE. These oils also provide protection against engine deposits, rust, and corrosion. Oils
meeting API Service Category SF may be used when API Engine Service Categories SE,
SD, or SC are recommended.
SG — 1989 Gasoline Engine Service (Obsolete) — Category SG denotes service typical
of gasoline engines in passenger cars, vans and light trucks operating under manufacturers'
recommended maintenance procedures. Category SG oils include the performance
properties of API Service Category CC. (Certain manufacturers of gasoline engines require
oils that also meet the higher diesel engine Category CD.) Oils developed for this service
provide improved control of engine deposits, oil oxidation, and engine wear relative to oils
developed for previous categories. These oils also provide protection against rust and
corrosion. Oils meeting API Service Category SG may be used when API Engine Service
Categories SF, SE, SF/CC, or SE/CC are recommended.
SH — 1994 Gasoline Engine Service — Category SH was adopted in 1992 to describe
engine oil first mandated in 1993. It is for use in service typical of gasoline engines in
present and earlier passenger cars, vans and light trucks operating under vehicle
manufacturers' recommended maintenance procedures. Engine oils developed for this
category provide performance exceeding the minimum requirements of API Service
Category SG, which it is intended to replace, in the areas of deposit control, oil oxidation,
wear, rust, and corrosion. Oils meeting API SH requirements have been tested according to
the Chemical Manufacturers Association (CMA) Product Approval Code of Practice and
may utilize the API Base Oil Interchange and Viscosity Grade Engine Testing Guidelines.
They may be used where API Service Category SG and earlier categories are
recommended. Effective August 1, 1997, API SH cannot be used except with API CF, CF-
2, CF-4 or CG-4 when displayed in the API service symbol, and the C category must
appear first.
SJ — 1997 Gasoline Engine Service — Category SJ was adopted in 1996 to describe
engine oil first mandated in 1997. It is for use in service typical of gasoline engines in
present and earlier passenger cars, vans and light trucks operating under vehicle
manufacturers' recommended maintenance procedures. Oils meeting API SJ requirements
have been tested according to the Chemical Manufacturers Association (CMA) Product
Approval Code of Practice and may utilize the API Base Oil Interchange and Viscosity
Grade Engine Testing Guidelines. They may be used where API Service Category SH and
earlier categories are recommended.
Engine Oil Classification System for Commercial Diesel Engine
Service
"C" — COMMERCIAL OILS
(FLEETS, CONTRACTORS, FARMERS, ETC.)
API Commercial
Engine Service
Categories
Previous API
Engine Service
Categories
Related Military or Industry
Designations
Engine Test Requirements
CA DG MIL-L-2104A CRC L-38; Caterpillar L-1* (0.4% sulfur)
CB DM MIL-L-2104A, Supplement 1 CRC L-38; Caterpillar L-1* (0.4% sulfur)
CC DM
MIL-L-2104B
MIL-L-46152B
CRC L-38; Sequence IID; Caterpillar 1H2*
CD DS
MIL-L-45199B, Series 3
MIL-L-2104C/D/E
CRC L-38; Caterpillar 1G2*
CD-II None MIL-L-2104D/E
CRC L-38; Caterpillar 1G2*; Detroit Diesel
6V53T
CE None None
CRC L-38; Caterpillar 1G2*; Cummins NTC-
400*; Mack T-6; Mack T-7
CF-4 None None
CRC L-38; Cummins NTC-400*; Mack T-6;
Mack T-7; Caterpillar 1K
CF-2 None None
CRC L-38; Caterpillar 1M-PC; Detroit Diesel
6V92TA
CF None None CRC L-38; Caterpillar 1M-PC
CG-4 None None
CRC L-38; Sequence IIIE; Roller Follower
Wear; Mack T-8; Caterpillar 1N
CH-4 None None
Sequence IIIE; Roller Follower Wear; Mack T-
8E; Mack T-9; Cummins M11; Caterpillar 1P;
Caterpillar 1K
* This test is obsolete; engine parts, test fuel, or reference oils are no longer generally
available, or the test is no longer monitored by the test developer or ASTM.
CA — Diesel Engine Service (Obsolete) — Service typical of diesel engines operated in
mild to moderate duty with high-quality fuels; occasionally has included gasoline engines
in mild service. Oils designed for this service provide protection from bearing corrosion
and ring-belt deposits in some naturally aspirated diesel engines when using fuels of such
quality that they impose no unusual requirements for wear and deposit protection. They
were widely used in the 1940s and 1950s but should not be used in any engine unless
specifically recommended by the equipment manufacturer.
CB — Diesel Engine Service (Obsolete) — Service typical of diesel engines operated in
mild to moderate duty, but with lower quality fuels, which necessitate more protection
from wear and deposits; occasionally has included gasoline engines in mild service. Oils
designed for this service were introduced in 1949. They provide necessary protection from
bearing corrosion and from high-temperature deposits in naturally aspirated diesel engines
with higher sulfur fuels.
CC — Diesel Engine Service (Obsolete) — Service typical of certain naturally aspirated,
turbocharged or supercharged diesel engines operated in moderate to severe-duty service,
and certain heavy-duty gasoline engines. Oils designed for this service provide protection
from high-temperature deposits and bearing corrosion in these diesel engines, and also
from rust, corrosion, and low-temperature deposits in gasoline engines. These oils were
introduced in 1961.
CD — Diesel Engine Service (Obsolete) — Service typical of certain naturally aspirated,
turbocharged or supercharged diesel engines where highly effective control of wear and
deposits is vital, or when using fuels with a wide quality range (including high-sulfur
fuels). Oils designed for this service were introduced in 1955 and provide protection from
high-temperature deposits and bearing corrosion in these diesel engines.
CD-II — Severe-Duty Two-Stroke Cycle Diesel Engine Service (Obsolete) — Service
typical of two-stroke cycle diesel engines requiring highly effective control of wear and
deposits. Oils designed for this service also meet all performance requirements of API
Service Category CD.
CE — 1983 Diesel Engine Service (Obsolete) — Service typical of certain turbocharged
or supercharged heavy-duty diesel engines, manufactured since 1983 and operated under
both low-speed, high-load and high-speed, high-load conditions. Oils designated for this
service may also be used when API Service Category CD is recommended for diesel
engines.
CF-4 — 1990 Diesel Engine Service — Service typical of high-speed, four-stroke cycle
diesel engines. API CF-4 oils exceed the requirements for the API CE category, providing
improved control of oil consumption and piston deposits. These oils should be used in
place of API CE oils. They are particularly suited for on-highway, heavy-duty truck
applications. When combined with the appropriate "S" category, they can also be used in
gasoline and diesel powered personal vehicles — i.e., passenger cars, light trucks, and vans
— when recommended by the vehicle or engine manufacturer.
CF — Indirect-Injected Diesel Engine Service — Service typical of indirect-injected
diesel engines and other diesel engines that use a broad range of fuel types, including those
using fuel with high sulfur content; for example, over 0.5% wt. Effective control of piston
deposits, wear and copper-containing bearing corrosion is essential for these engines,
which may be naturally aspirated, turbocharged or supercharged. Oils designated for this
service have been in existence since 1994 and may be used when API Service Category
CD is recommended.
CF-2 — Severe-Duty Two-Stroke Cycle Diesel Engine Service — Service typical of
two-stroke cycle diesel engines requiring highly effective control over cylinder and ringface
scuffing and deposits. Oils designed for this service have been in existence since 1994
and may also be used when API Engine Service Category CD-II is recommended. These
oils do not necessarily meet the requirements of API CF or CF-4 unless they pass the test
requirements for these categories.
CG-4 — 1994 Severe-Duty Diesel Engine Service — API Service Category CG-4
describes oils for use in high-speed four-stroke-cycle dieselengines used in both heavyduty
on-highway (0.05% wt sulfur fuel) and off-highway (less than 0.5% wt sulfur fuel)
applications. CG-4 oils provide effective control over high-temperature piston deposits,
wear, corrosion, foaming, oxidation stability, and soot accumulation. These oils are
especially effective in engines designed to meet 1994 exhaust emission standards and may
also be used in engines requiring API Service Categories CD, CE, and CF-4. Oils designed
for this service have been in existence since 1994.
CH-4— 1998 Severe-Duty Diesel Engine Service— API Service Category CH-4 oils are
suitable for high-speed, four-stroke diesel engines designed to meet 1998 exhaust emission
standards and are specifically compounded for use with diesel fuels ranging in sulfur
content up to 0.5% weight. CH-4 oils are superior in performance to those meeting API
CF-4 and API CG-4 and can effectively lubricate engines calling for those API Service
Categories.
Klasifikasi menurut SAE
SAE (Society of Automotive Engineer) mengeluarkan klasifikasi pelumas mesin seperti
tabel dibawah..
No Tingkat
viskosit
as SAE
Viskositas
kinematik
min.
@ -18C
(cSt)
Viskositas
kinematik
mak.
@ -18C
(cSt)
Viskositas
kinematik
min.
@ 98,9C
(cSt)
Viskositas
kinematik
mak.
@ 98,9C
(cSt)
1 5W - 869 - -
2 10W 1303 2606 - -
3 20W 2603 10243 - -
4 20 - - 5.73 9.62
5 30 - - 9.62 12.93
6 40 - - 12.93 16.77
7 50 - - 16.77 22.68
Minyak lumas "multigrade" yaitu minyak lumas yang memenuhi dua atau lebih tingkatan
viskositas dari SAE, misalnya SAE 20W-40 digunakan di daerah iklim sedang. . Minyak
lumas "singlegrade", SAE-30, SAE-40 dipergunakan di daerah iklim tropis
INDUSTRIAL LUBRICANTS
There are many kind of indudtrial lubricant, some of them are listed below
Concrete Form Oil
Lubricants which are formulated to provide a clean, quick release of the plywood,
metal, or plastic forms from concrete after setting. Usually available in a light viscosity to
accommodate spraying of the lubricant on the forms.
Cutting Oils
The main functions of a cutting oil are to lubricate or reduce friction between the
tool and the workpiece, and to act as a coolant by rapidly removing heat generated at the
tool-workpiece interface.
Soluble cutting oils are mixed with water in proportions of 3 to10%. They are used where
rapid heat removal is a major requirement. Usually formulated with emulsifiers, rust
inhibitors, and EP additives.
Insoluble cutting oils are used in operations involving tough cutting such as tapping,
threading, and broaching. Lubricity and anti-weld characteristics are important
characteristics of this cutting oil.
Chain Oil
These oils are formulated to lubricate saw chains, and should provide the following
benefits:
• An unbroken film of lubricant between chain links and bars.
• Anti-wear characteristics to prevent chain and bar wear.
• Chain oil should have throw-off resistance. Classified as "tacky".
• Prevent corrosion of the chain.
Tip! The winter grade may be used as an air filter coating where a tacky product is
required for dust removal.
Compressor Oil
Oils which are formulated for use in reciprocating and rotary air compressors. Available in
different viscosity grades for use in different ambient temperature ranges.
Heat Transfer Fluids
A lubricant used as a heat transfer medium in applications such as:
• Plastic extrusion machines.
• Textile dryers.
• Die casting.
Some high quality heat transfer fluids can provide clean, odorless operation up to
temperatures of 326°C. Petro Canada has a product named CALFLO which is a unique
semi-synthetic heat transfer fluid.
Hydraulic Oil
Hydraulic systems provide a means to transfer power where gears are impractical. A
typical system includes a reservoir for the hydraulic fluid, a pump, transfer hoses, and
return hoses to the reservoir.
The important characteristics of a hydraulic fluid are:
• Thermal stability
• Corrosion protection
• Anti-wear properties
• Anti-foaming properties
The oil is available in different viscosity grades to accommodate a variety of ambient
operating temperatures.
Industrial Gear Lubricants
These oils provide protection to different types of industrial gears which are often operated
under high contact pressures, and intermittent shock-loading. Gear lubricants often contain
an EP (Extreme Pressure) Additive.
A wide variety of ISO viscosity grades are available from your supplier
Refrigeration Lubricant
This lubricant is used in commercial refrigeration compressor systems.
This oil is available in two formulations:
1. For use in CFC (chlorinated fluorocarbon) systems.
2. For use in ammonia refrigeration systems.
GREASE
Grease can be defined as a solid to semi-solid material produced by the dispersion
of a thickening agent in a liquid lubricant. Other ingredients may be included to impart
special properties to the grease.
Thickener Lubricating Oil Additives
5 - 20% 75 - 95% 0-15%
Complex Grease
A complex grease is similar to a regular grease except that the thickener contains two
dissimilar fatty acids, one of which is the complex agent. This results in good high
temperature characteristics to the final product.
Lubricating Oil
Because of the high percentage of oil by weight in grease, the oil must be of high quality
and the proper viscosity. Light viscosity oils are used for low temperature, low load, and
high speed applications. Conversely, a heavy viscosity oil is generally used for high
temperature, high load, and slow speed application.
Additives
The most common additives found in grease are as follows:
• Oxidation Inhibitors
• EPA Agents
• Anti-Corrosion Agents
• Anti-Wear Agents
Grease Characteristics
The most important factors affecting the properties and characteristics of a grease are:
• Amount and type of thickener
• Oil viscosity and physical characteristics
• Additives
A grease is expected to:
• Reduce friction and wear
• Provide corrosion protection
• Seal bearings from water and contaminants
• Resist leakage, dripping, and throw-off
• Be compatible with seals
• Repel moisture
Grease Definitions
Consistency-is the degree of hardness of a grease and may vary considerably with
temperature. This has been classified by the National Lubricating Grease Institute
(N.L.G.I.) into the following categories:
N.L.G.I. GRADE PENETRATION @ 25°c(1/10th mm)
000 445-475
00 400- 30
0 355-385
1 310-340
2 265-295
3 220-250
4 175-205
5 130-160
6 85-115
Shear Stability - is the ability of a grease to resist a change in consistency during
mechanical working. Under high rates of shear, grease structures tend to change in
consistency.
Oil Separation - is the percentage of oil which separates from the grease under storage
conditions. It cannot predict separation tendencies in use under dynamic conditions
High Temperature Stability - is the ability of a grease to retain its consistency, structure,
and performance at temperatures in excess of 125°ree;C
Grease Properties
The following chart is designed to help you select a type of grease that will satisfy the
intended application.
Properties Calcium Lithium Sodium
Aluminum
Complex
Calcium
Complex
Barium
Complex
Lithium
Complex
Polyurea
Synthetic
Bentone
Clay
Dropping Point °C 80-100 175-205
170-
200
260+ 260+ 200+ 260+ 250+ None
Max Temp°C 65 125 125 150 150 150 160 150 150
High Temp Use V.Good Good Good Exc Exc Good Exc Exc Exc
Low Temp
Mobility
Fair Good Poor Good Fair Poor Good Good Good
Mech. Stability Fair Good Fair Exc Good Fair Exc Good Fair
Water Resistance Exc Good Poor Exc Exc Exc Exc Exc Fair
Oxidation Stability Poor Good Good Exc Exc Poor Good Exc Good
Texture Smooth Smooth Smooth Smooth Smooth Fibrous Smooth Smooth Smooth
5. DEGRADATION Of LUBRICANT
How of Oxidation Testing
It is widely understood that oxidation is the primary mechanism of lubricant
degradation. It is also widely known that oxidized oil can’t effectively lubricate machines;
oil analysis tests like Total Acid Number and FTIR-Oxidation can reveal abnormal
oxidation. Less widely understood is how these tests monitor the onset and propagation of
oxidation, and the significance of the results. It is important for lubrication and oil analysis
technologists to understand how lubricant oxidation is measured, and how these tests can
best be applied to monitor the lubricant’s performance. A greater understanding of
lubrication oxidation will enable technologists to make informed decisions to ensure
lubrication excellence.
The Chemistry of Oil Oxidation
The fundamental key to understanding lubricant oxidation is having basic knowledge of
the chemistry of lubricants and their degradation. The chemistry of lubricants is simply a
specialized sub-set of organic chemistry. Organic chemistry is the study of carbon-based
compounds and their reactions. Lubricant base oils, with a few exceptions, are classified as
organic compounds because they are primarily hydrocarbons. Base-oil oxidation is an
example of the many possible organic reactions that can occur in a lubricant. To fully
understand the oxidation of lubricants, we first consider the generic reaction of
hydrocarbon oxidation.
A hydrocarbon is a compound containing carbon and hydrogen. Although there are an
infinite number of variations and complexities in the final compounds, a basic hydrocarbon
structure can be represented in Figure 1.
In Figure 1, the black spheres represent carbon atoms, and the smaller white spheres
represent hydrogen atoms. The links between the carbon and hydrogen atoms represent
bonds that attract and hold the atoms together. This bonded structure is referred to as a
compound. The number of carbons and the type of bonding present characterize a
hydrocarbon compound. The compound represented in Figure 1 is n-Heptane, a common
liquid hydrocarbon used as a reagent in some oil analysis tests.
Common lubricants are made up of compounds with longer chains and multiple bonding
configurations. When describing the chemistry of lubricants and their reactions, it will
usually suffice to show just the end of the molecule, or some part of a chain with the letter
R representing an undefined chain of carbons, hydrogens and other atoms (see Figure 2).
For the purposes of studying the oxidative reaction of the compound, the R is unimportant,
since it does not factor into the reaction.
The most important chemical reaction of a hydrocarbon, for a lubrication engineer or
analyst, is oxidation. Oxidation of hydrocarbons is commonly referred to as combustion or
“burning.” When one burns paper, wood, natural gas or fuel oil, for example, hydrocarbons
are oxidized. In a well-designed burner, propane gas undergoes complete combustion. This
means that all carbons are completely oxidized; all hydrogens bonded to carbons are
replaced by oxygens, therefore producing CO2 and H2O. The reaction is illustrated in
Figure 3 where five oxygen molecules (O2) completely oxidize the illustrated hydrocarbon
to produce three carbon dioxide molecules and four water molecules.
Complete combustion requires relatively high temperatures, a pure fuel source and an
ample supply of oxygen. Most combustion reactions found in nature, however, are not
complete, and result in various other products in addition to CO2 and H2O, as illustrated
above. Incomplete combustion of the hydrocarbon chain of a lubricant can produce
carboxylic acid (Figure 4) and other impurities.
The double-link between the carbon atom and the top oxygen atom represents a double
bond. This reaction illustrated in Figure 4 occurred at the end of a chain. Oxidation can
also occur in the middle of the chain, splitting the hydrocarbon into two Carboxylic Acids
as illustrated in Figure 5. In this case R represents some undefined chain and R1 represents
a different chain but are unimportant because they are not involved in the reaction.
The Effect of Oxidation on Lubricant Properties
The most important reaction on lubricant properties is when a single chain is broken down
into two smaller chains. This is when the chemical reaction of oxidation begins to
transform the physical world of lubrication. There is no noticeable difference once this
reaction starts to lubricate a bearing. However, a significant change can be observed when
this oxidation reaction has occurred on a large percentage of the molecules in that
reservoir.
By breaking down the chain, the ability of that molecule to carry the load between two
moving solid surfaces has been altered. Additionally, the new shape of the molecules will
cause them to interact in a different physical manner with the normal lubricant molecules,
and can result in a greater than normal viscous heating. Imagine a room covered with a
single layer of uniform marbles and then lay a flat board on top of them. The board will
slide around fairly easily because the marbles act like ball bearings. But if you were to add
a few ping-pong balls to the room, the board would not move as smoothly; there is
increased friction caused by the presence of the Ping-Pong balls.
The increases in viscosity that are seen as a result of oxidation can be explained by
pointing to the polymerization of products such as sludge. However, with only the
mechanism of oxidative cleaving of hydrocarbon chains, there can be a net effect of
increased viscosity due to the strained interaction of non-homogeneous compounds in the
lubricant. Just like Ping-Pong balls interfere with the relative motion of a board moving
across marbles, non-homogenous molecules impede the relative motion of fluid. Where
previously the molecules in the oil were similar in size and shape and flowed fairly freely
among each other, the new compounds created from oxidation are quite different and
introduce new forces of interaction between the molecules. For instance, carboxylic acid
compounds can be highly associated, meaning that there is an attraction between the
molecules, causing them to behave as a larger molecule. (See Figure 6)
his associated molecule is known as a dimer, and is suggested in lubricants by the
occurrence of the carboxylic acid carbonyl peak on the infrared spectrum. In oxidized
lubricants, the peak is seen at 1710 cm-1, indicative of an associated carbonyl, instead of
the unassociated peak at 1760 cm-1. The net effect is a greater resistance to flow at the
molecular level, which can have the bulk effect of a viscosity increase in the lubricating
fluid.
Oil Analysis Indications of Lubricant Oxidation
The oil produces numerous warning signals indicating oxidation that can be detected with
oil analysis. Below is a review of the most common warning signals.
Total Acid Number (TAN) - As previously discussed, organic acids are produced during
oxidation. These acids are detectable as an increase in the TAN number which quantifies
acid concentration by measuring the volume of an alkaline (potassium hydroxide) reagent
that is required to neutralize the acid in the oil. The TAN test doesn’t discriminate acids
generated by oxidation from those that are ingested as contaminants from the process.
Also, some additives like anti-wear, extreme pressure and some rust inhibitors, are acidic.
They produce a high initial TAN that can diminish as the additive is depleted.
Viscosity - As carboxylic acid byproducts of oxidation dimerize (or associate), the median
density of the molecules increases. This results in increased viscosity. Viscosity can be
measured using kinematic or absolute methods.
Fourier Transform Infrared (FTIR) Spectroscopy - This technique involves passing a
beam of infrared energy through a sample of oil. Different molecules absorb infrared
energy at different frequencies. As the oil oxidizes, hydrocarbons transition to aldehydes,
ketones, alcohols and carboxylic acids that are detectable by the FTIR
spectrometer as new compounds.
Darkening Color - For various reasons, as the oil oxidizes, its color tends to darken.
While dark oil is not always oxidized and degraded, it is one possible indication.
Foul Odor - As the oil oxidizes, it often assumes a putrid odor. If the base-oil contains
sulfur components, or the oil is equipped with a sulfur-containing additive, the odor may
resemble that of a rotten egg.
Conclusions
Lubricant oxidation is serious business. Not only is the lubricant’s performance
diminished, the acids produced can increase corrosive component wear. It is important to
understand the process and root causes of oxidation and the warning signals generated by
oil analysis. Managing and measuring lubricant oxidation is the key to the pursuit of
lubrication excellence.
Oxidation mechanism of oil
Engine lubricants are generally used to reduce friction between moving parts within the
interior engine. In addition to the lubricating function, motor oil also serves as a coolant,
corrosion protector, and method of removing contaminants from the engine filter. In other
words, motor oil holds the same importance to an engine that blood holds for humans. Loss
of any essential function of the motor oil will lead to serious engine damage. Through the
oxidation of motor oil, its essential functions are destroyed. This degradation usually
begins cause severe engine damage after approximately 100,000 miles (Fogler and
LeBlanc, p.15).
As lubricants degrade, their physical properties (e.g. viscosity) change, leading to
increased friction and wear. This degradation is primarily due to base oil oxidation. Base
oil is the petroleum component of the lubricant. Generally, the base oil comprises eighty
percent of the lubricant, with the remainder being additives.
The following reaction mechanisms describe the oxidation and degradation of an engine
lubricant under four different conditions:
X low temperature, no additives (antioxidants)
X high temperature, no additives
X low temperature, additives present
X high temperature, additives present
Low Temperatures, No Antioxidants
High Temperatures, No Antioxidants
Above equations, plus...
Low and High Temperatures With Antioxidants
Above equations pertaining to whichever temperature you're figuring, plus...
The four different conditions must be analyzed separately because as temperature
changes, the physical characteristics, along with the reaction rate and reaction
extent change. Also, the presence of antioxidant additives reduces the oxidation
of the base oil.
USED OIL RECYCLING
Used oil, or 'sump oil' as it is sometimes called, should not be thrown away.
Although it gets dirty, used oil can be cleaned of contaminants so it can be recycled again
and again. There are many uses for recycled used oil. These include:
• X Industrial burner oil, where the used oil is dewatered, filtered and demineralised
for use in industrial burners;
• X Mould oil to help release products from their moulds (e.g. pressed metal
products, concrete);
• X Hydraulic oil;
• X Bitumen based products;
• X An additive in manufactured products; or
• X Re-refined base oil for use as a lubricant, hydraulic or transformer oil.
Once you have taken your used oil to your local collection facility, used oil collectors
take the used oil and undertake some pre-treatment and recycling of the used oil or sell it to
a specialised used oil recycler.
Pre-treatment
Dewatering. One way of doing this is by placing it in large settling tanks, which separates
the oil and water.
Further recycling steps include:
• Filtering & demineralisation of the oil, to remove any solids, inorganic material and
certain additives present in the oil, producing a cleaner burner fuel or feed oil for
further refining;
• Propane de-asphalting to remove the heavier bituminous fractions, producing rerefined
base oil; and
• Distillation to produce re-refined base oil suitable for use as a lubricant, hydraulic
or transformer oil. This process is very similar to the process undergone by virgin
oil.
Pre-treatment or Dewatering
Water is found in used oil as free water or bound water, for example in emulsions. The
term dewatering is usually taken to mean the removal of free water. Where water has been
emulsified with oil, the emulsion has to be "broken" with a demulsifier before the water
can be separated from the oil.
Dewatering is a simple process relying on the separation of aqueous and oil phases over
time under the influence of gravity. The used oil is allowed to stand in a tank (raw waste
oil) and free water drops to the bottom where it can be drained, treated (waste water
treatment) and discharged appropriately to sewer or stormwater depending on quality and
local regulations.
Heating and stirring the used oil in a tank (A) and driving off the water through
evaporation can speed up the dewatering process.
The "dried" or dehydrated oil is then suitable for further processing or for use as a burner
fuel.
Filtering & Demineralisation
The purpose of filtering and demineralisation is to remove inorganic materials and certain
additives from used oil to produce a cleaner burner fuel or feed for re-refining.
Used oil feedstock is transferred to a reaction tank (A) and mixed with a small quantity of
sulphuric acid and heated to about 60oC. A chemical surface-active reagent, called a
surfactant, is added to the reactor (A) and after stirring the mixture is allowed to stand.
This allows the mixture to separate into two "phases" - i.e. oil and water-based or aqueous.
The reagent causes the contaminants to accumulate in the aqueous phase, which settles to
the bottom of the tank (A) and is drained off as slurry. This phase contains acid, used oil
contaminants, including metals and some of the oil additives. The water is dried off,
leaving a solid waste that must be disposed of.
The demineralised oil is filtered (B) to remove suspended fine particles (to solid waste) and
run off to storage (C) as a clean burner fuel. It can be further diluted or "cut" with a lighter
petroleum product (called cutter stock) to produce a range of intermediate to light fuel oils
depending on the fuel viscosity requirements of the burner.
Propane De-asphalting
The Propane De-asphalting (PDA) process is an important pre-treatment step in the rerefining
process producing de-asphalted lube-oil, which becomes a feedstock for the next
step in a re-refining facility. The other output (which is also an input) is propane, which is
recovered from both streams and re-used within the process.
The PDA process relies on the greater solubility of the paraffinic and naphthenic (ie
essentially the base oil) components versus the contaminated waste material in a stream of
propane.
The separation of the lubricating oil fraction from used oil is a continuous process and is
conducted at ambient temperature when processing used oil.
The used oil is pumped into the middle of the extraction column (A). Liquid propane is
charged to the bottom of the column (A). The oil being heavier than propane, flows down
the column (A); the propane rises in a counter-flow thus mixing the input streams within
the column (A). The rising propane dissolves the more soluble lube oil components, which
are carried out the top of the column (A) with the propane, and the propane insoluble
material is removed from the bottom of the column (A).
Propane is vaporised from both streams [ie., the de-asphalted lube-oil stream (B) and the
waste stream (C)] in "stripper" units (B) and (C), then condensed and returned to the
propane storage tank.
The de-asphalted lube-oil component is feed for the next processing stage. The residuum
(waste) component is mixed with bottoms from the vacuum distillation tower to produce
an asphaltic material.
Distillation
Distillation (or Fractionation) is the physical separation of components of lubricating oil by
boiling range. Depending on the type of distillation, the boiling ranges can produce gases
and gasolines at the lower boiling points with heavy lubricating oils being distilled at
higher boiling points. Distillation is the core process for a facility capable of producing rerefined
base-oils to virgin base-oil quality.
There are 2 types of distillation, atmospheric and vacuum.
Atmospheric Distillation
Atmospheric distillation is generally (but not always) considered a pre-treatment step for
vacuum distillation and does not require de-watered feedstock. Atmospheric distillation is
carried out at normal atmospheric pressure and with temperatures up to 300°C.
Prior to the atmospheric distillation process, the feedstock can have undergone PDA
treatment, but this is not an absolute pre-requisite.
Atmospheric distillation is a relatively simple process separating lower boiling point
liquids at ambient pressure. Used oil is heated (A) and charged to a distillation tower (B).
Lower boiling point hydrocarbons present in the used oil (eg gases, petrol and solvents)
and water are collected at the top of the tower (B). Some of these hydrocarbons can be
condensed and collected for use as a fuel in the refining process.
This process is only suitable for temperatures up to 300oC, as temperatures above this can
lead to "thermal cracking" of the larger molecule (higher boiling point) hydrocarbons, ie.
the actual lube oil molecules we are aiming to recover.
After atmospheric distillation the oil usually undergoes vacuum distillation. Note that used
oil can be sent directly from a "drying" process to a vacuum distillation unit without
necessarily undergoing atmospheric distillation. However, it is generally accepted that
water and lower boiling point hydrocarbon components be removed prior to vacuum
distillation.
Vacuum Distillation
Vacuum distillation is considered the key process in used oil re-refining. If atmospheric
distillation is utilised, the oil from the atmospheric distillation column is the feedstock for
the vacuum distillation column. In vacuum distillation the feedstock can be separated into
products of similar boiling range to better control the physical properties of the lube base
stock "distillate cuts" that will be produced from the vacuum tower products.
The major properties that are controlled by vacuum distillation are viscosity, flash point
and carbon residue. The viscosity of the lube-oil base-stock is determined by the viscosity
of the distillate in terms of its relative viscosity separation, eg. light, medium and heavy
oil.
The used oil feedstock (usually from the atmospheric distillation unit) is heated in a
furnace (A) and flows as a mixture of liquid and vapour to the heated vacuum distillation
column (B) where the vapour portion begins to rise and the liquid falls. Steam can be
added to assist vaporisation.
A vacuum is maintained in the column (2-10 mm Hg) by a vacuum system connected to
the top of the tower (B). By reducing the pressure, materials normally boiling at up to
about 540oC at atmospheric pressure, can be vaporised without thermal cracking.
As the hot vapours rise through the column (B), they cool and some condense to a liquid
and flow back down the column. Similarly, some of the downward flowing liquids are revaporised
by contacting the rising hot vapours. Special devices in the column allow this
upward flow of vapours and downwards flow of liquids to occur continuously.
At various points in the column (B), special trays, called draw trays, are installed which
permit the removal of the liquid from the column. If three cuts or "fractions" of oil are
required to produce light, medium and heavy base stocks, then three draw trays are
positioned appropriately. This can be reduced to two draw trays if, for example, only 2 cuts
or fractions are required.
Some of the material does not boil even under this vacuum. This remains in the vacuum
tower and is run out as the vacuum tower bottoms (VTBs). This material contains the
heaviest molecules, including some lube oil additives and carryover contaminants not
removed in the PDA process. (Note: not all re-refining plants have PDA units).