Lubrication Fundamentals, Revised and Expanded

Don M. Pirro, Martin Webster, Ekkehard Daschner

• Publisher: CRC Press
• Year: 2017
• ISBN:
  9781315359908
• Edition: 3
• Topic: Physical Sciences
• Subtopic: Industrial & Technical Chemistry

Careful selection of the right lubricant(s) is required to keep a machine running smoothly. Lubrication Fundamentals, Third Edition, Revised and Expanded describes the need and design for the many specialized oils and greases used to lubricate machine elements and builds on the tribology and lubrication basics discussed in previous editions.

Utilizing knowledge from leading experts in the field, the third edition covers new lubrication requirements, crude oil composition and selection, base stock manufacture, lubricant formulation and evaluation, machinery and lubrication fundamentals, and environmental stewardship. The book combines lubrication theory with practical knowledge, and provides many useful illustrations to highlight key industrial, commercial, marine, aviation, and automotive lubricant applications and concepts. All previous edition chapters have been updated to include new technologies, applications, and specifications that have been introduced in the past 15 years.

What's New in the Third Edition:

• Adds three new chapters on the growing renewable energy application of wind turbines, the impact of lubricants on energy efficiency, and best practice guidelines on establishing an in-service lubricant analysis program
• Updates API, SAE, and ACEA engine oil specifications, descriptions of new engine oil tests, impact of engine and fuel technology trends on engine oil
• Includes the latest environmental lubricant tests, definitions, and labelling programs
• Compiles expert information from ExxonMobil publications and the foremost international equipment builders and industry associations
• Covers key influences impacting lubricant formulations and technology
• Offers data on global energy demand and interesting statistics such as the worldwide population of nuclear reactors, wind turbines, and output of hydraulic turbines
• Presents new sections on the history of synthetic lubricants and hazardous chemical labeling for lubricants

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Whether used as a training guide for industry novices, a textbook for students to understand lubrication principles, or a technical reference for experienced lubrication and tribology professionals, Lubrication Fundamentals, Third Edition, Revised and Expanded is a "must read" for maintenance professionals, lubricant formulators and marketers, chemists, and lubrication, surface, chemical, mechanical, and automotive engineers.

1	Introduction

Petroleum is one of the naturally occurring hydrocarbons that frequently include natural gas, natural bitumen, and natural wax. The name “petroleum” is derived from the Latin petra (rock) and oleum (oil). According to the most generally accepted theory today, petroleum was formed by the decomposition of organic refuse, aided by high temperatures and pressures, over a vast period of geologic time.

I. PREMODERN HISTORY OF PETROLEUM

Although petroleum occurs, as its name indicates, among rocks in the earth, it sometimes seeps to the surface through fissures or is exposed by erosion. The existence of petroleum was known to primitive man, as surface seepage, often sticky and thick, was obvious to anyone passing by. Prehistoric animals were sometimes mired in it, but few human bones have been recovered from these tar pits. Early man evidently knew enough about the danger of surface seepage to avoid it.

The first actual use of petroleum seems to have been in Egypt, which imported bitumen, probably from Greece, for use in embalming. The Egyptians believed that the spirit remained immortal if the body was preserved.

Around the year 450 B.C., Herodotus, widely referred to as the father of history, described the pits of Kir A’b near Susa in present-day Iraq as follows:

At Ardericca is a well which produces three different substances, for asphalt, salt and oil are drawn up from it in the following manner. It is pumped up by means of a swipe; and, instead of a bucket, half a wine skin is attached to it. Having dipped down with this, a man draws it up and then pours the contents into a reservoir, and being poured from this into another, it assumes these different forms: the asphalt and salt immediately become solid, and the liquid oil is collected. The Persians call it Phadinance; it is black and emits a strong odor.

Pliny, the historian, and Dioscorides Pedanius, the Greek botanist, both mention “Sicilian oil,” from the island of Sicily, which was burned for illumination as early as the beginning of the Christian Era.

The Scriptures contain many references to petroleum, in addition to the well-known story of Moses, who was set afloat on the river as an infant in a little boat of reeds waterproofed with pitch, and was found by Pharaoh’s daughter. Some of these references include the following:

Make thee an ark of gopher wood; rooms shalt thou make in the ark, and shalt pitch it within and without with pitch. (Genesis VI.14)
And they had brick for stone, and slime (bitumen) had they for mortar. (Building the Tower of Babel, Genesis XI.3)
And the Vale of Siddim was full of slime (bitumen) pits; and the kings of Sodom and Gomorrah fled, and fell there.… (Genesis XIV.10)

Other references are found in Strabo, Josephus, Diodorus Siculus, and Plutarch, and since then there is substantial evidence that petroleum was known in almost every part of the world.

Marco Polo, the Venetian traveler and merchant, visited the lands of the Caspian in the thirteenth century. In an account of this visit, he stated:

To the north lies Zorzania, near the confines of which there is a fountain of oil which discharges so great a quantity as to furnish loading for many camels. The use made of it is not for the purpose of food, but as an unguent for the cure of cutaneous distempers in men and cattle, as well as other complaints; and it is also good for burning. In the neighboring country, no other is used in their lamps, and people come from distant parts to procure it.

Sir Walter Raleigh, while visiting the island of Trinidad off the coast of Venezuela, inspected the great deposit of bitumen there. The following is taken from The Discoveries of Guiana (1596):

At this point called Tierra de Brea, or Piche, there is that abundance of stone pitch that all the ships of the world may be therewith loden from thence, and wee made triall of it in trimming our ships to be most excellent good, and melteth not with the sunne as the pitch of Norway, and therefore for ships trading the south partes very profitable.

II. PETROLEUM IN NORTH AMERICA

In the North American continent, petroleum seepages were undoubtedly known to the aborigines, but the first known record of the substance was made by the Franciscan friar, Joseph de la Roche D’Allion, who in 1629 crossed the Niagara River from Canada and visited an area later known as Cuba, New York. At this place, petroleum was collected by the Indians, who used it medicinally and to bind pigments used in body adornments.

In 1721, Charlevois, the French historian and missionary who descended the Mississippi River to its mouth, quotes a Capitan de Joncaire as follows:

There is a fountain at the head of a branch of the Ohio River (probably the Allegheny) the waters of which like oil, has a taste of iron and serves to appease all manner of pain.

In the Massachusetts Magazine, Volume 1, July 1789, there is an account under the heading “American Natural Curiosities,” as follows:

In the northern parts of Pennsylvania, there is a creek called Oil Creek, which empties into the Allegheny River. It issues from a spring, on the top of which floates an oil similar to that called Barbadoes tar; and from which one man may gather several gallons in a day. The troops sent to guard the western posts halted at this spring, collected some of the oil, and bathed their joints with it. This gave them great relief from the rheumatic complaints with which they were affected. The waters, of which the troops drank freely, operated as a gentle purge.

Although the practice of deriving useful oils by the distillation of bituminous shales and various organic substances was generally known, it was not until the nineteenth century that distillation processes were widely used for a number of useful substances, including tars for waterproofing; gas for illumination; and various chemicals, pharmaceuticals, and oils.

In 1833, Dr. Benjamin Silliman contributed an article to the American Journal of Science that contained the following:

The petroleum, sold in the Eastern states under the name of Seneca Oil, is a dark brown color, between that of tar and molasses, and its degree of consistency is not dissimilar, according to temperature; its odor is strong and too well known to need description. I have frequently distilled it in a glass retort, and the naphtha which collects in the receiver is of a light straw color, and much lighter, more odorous and inflammable than the petroleum; in the first distillation, a little water usually rests in the receiver, at the bottom of the naphtha; from this it is easily decanted, and a second distillation prepares it perfectly for preserving potassium and sodium, the object which led me to distil it, and these metals I have kept under it (as others have done) for years; eventually they acquire some oxygen, from or through the naphtha, and the exterior portion of the metal returns, slowly, to the condition of alkali—more rapidly if the stopper is not tight.

The petroleum remaining from the distillation is thick like pitch; if the distillation has been pushed far, the residuum will flow only languidly in the retort, and in cold weather it becomes a soft solid, much resembling the maltha or mineral pitch.

Along the banks of the Kanawha River in West Virginia, petroleum was proving a constant source of annoyance in the brine wells; and one of these wells, in 1814, discharged petroleum at periods of from 1 to 4 days, in quantities ranging from 30 to 60 gallons at each eruption. A Pittsburgh druggist named Samuel M. Kier began bottling the petroleum from these brine wells about 1846 and selling the oil for medicinal purposes. He claimed it was remarkably effective for most ills and advertised this widely. In those days, many people believed that the worse a nostrum tasted, the more powerful it was. People died young then, and often did not know what killed them. In the light of today’s knowledge, we would certainly not recommend drinking such products. Sales boomed for awhile, but in 1852, there was a falling-off in trade. Therefore, the enterprising Mr. Kier began to distill the substance for its illuminating oil content. His experiment was successful and was a forerunner, in part, of future commercial refining methods.

In 1853, a bottle of petroleum at the office of Professor Crosby of Dartmouth College was noticed by Mr. George Bissel, a good businessman. Bissel soon visited Titusville, Pennsylvania, where the oil had originated, and purchased 100 acres of land in an area known as Watsons Flats and leased a similar tract for the total sum of $5000. Bissel and an associate, J.D. Eveleth, then organized the first oil company in the United States, the Pennsylvania Rock Oil Company. The incorporation papers were filed in Albany, New York, on December 30, 1854. Bissel had pits dug in his land in the hope of obtaining commercial quantities of petroleum, but was unsuccessful with this method. A new company was formed, which was called the Pennsylvania Rock Oil Company of Connecticut, with New Haven as headquarters. The property of the New York corporation was transferred to the new company, and Bissel began again.

In 1856, Bissel read one of Samuel Kier’s advertisements on which was shown a drilling rig for brine wells. Suddenly it occurred to him to have wells drilled, as was being done in some places for brine. A new company, the Seneca Oil Company, succeeded the older company, and an acquaintance of some of its partners, E.L. Drake, was selected to conduct field experiments in Titusville. Drake found that, to reach hard rock in which to try the drilling method, some unusual form of shoring was needed to prevent a cave-in. It occurred to him to drive a pipe through the loose sand and shale—a plan afterward adopted in oil well and artesian well drilling.

Drilling then began under the direction of W.A. Smith, a blacksmith and brine well driller, and went down 69 1/2 ft. On Saturday, August 27, 1859, the drill dropped into a crevice about 6 inches deep, and the tools were pulled out and set aside for the work to be resumed on Monday. However, Smith decided to visit the well that Sunday to check on it, and upon peering into the pipe saw petroleum within a few feet of the top. On the following day, the well produced the incredible quantity of 20 barrels of oil a day.

III. DEVELOPMENT OF LUBRICANTS

James Watt’s development of the practical steam engine, circa 1769, introduced the industrial age. The coming of new, more demanding machines, in turn, marked the beginning of the search for improved lubricants. They were needed to meet the requirements of devices operating at constantly increasing speeds and loads. The first substances to be used were mineral oils, which were obtained from naturally occurring surface pools and extended with the addition of the already known plant and animal oils.

During the period from 1850 to 1875, many men experimented with the products of petroleum distillation then available, attempting to find uses for them, in addition to providing illumination. Some of the viscous materials were investigated as substitutes for the vegetable and animal oils previously used for lubrication, mainly those derived from olives, rape seed, whale, tallow, lard, and other fixed oils.

As early as 1400 B.C., greases, made of a combination of calcium and fats, were used to lubricate chariot wheels. Traces of this grease were found on chariots excavated from the tombs of Yuaa and Thuiu. During the third quarter of the nineteenth century, greases were made with petroleum oils combined with potassium, calcium, and sodium soaps and placed on the market in limited quantities.

Gradually, as distillation and refining processes were improved, a wider range of petroleum oils were produced to take the place of the fatty oils. These mineral oils could be controlled more accurately in manufacture and were not subject to the rapid deterioration of the fatty oils.

The latter half of the nineteenth century saw the development of many new techniques for the most efficient production of lubricants from petroleum. Not the least of these was vacuum distillation, first put to commercial use by Vacuum Oil Company of Rochester, New York, successor to Mobil Oil Corporation and present-day ExxonMobil Corporation. This process permitted the distillation of crude residuum without the use of destructively high temperatures. What set vacuum-distilled lubricants apart was reliability as machines started easier, lasted longer, and had fewer problems.

In the early 1900s, gasoline became important, and this resulted in ever-increasing demands for crude oil. Until this time, only Pennsylvania crudes were used for lubricating oil but now new processes were developed to make lube stocks from other crude sources. Some of the fatty oils continued to be used in special services as late as the early part of the twentieth century. Tallow was fairly effective in steam cylinders as a lubricant. However, it was not always pleasant to handle, because maggots developed in the tallow particularly in hot weather. Lard oil was used for cutting of metals, and castor oil was used to lubricate the aircraft engines of World War I. Even today, some fatty oils are still used as compounding in small percentages with mineral oils, but chemical additives have taken their place for the majority of users.

During the period 1910–1918, improved mechanical equipment—e.g., high-pressure steam turbines, new electrical machinery, and automobiles, placed greater demands on lubricants. Thus began the first real growth in lubricants research. This covered both refining and the new field of additive technology. It carried on, with a high level of intensity, through the 1920s and 1930s, reaching its peak during World War II. Always the impetus was the same: new innovations in machine design required new innovations in lubricant composition.

IV. HISTORY OF SYNTHETIC LUBRICANTS

A historical survey of the development of synthetic lubricants would be incomplete if it did not include mention of those oils and fats that occur in nature. In the grave of the Egyptian Tehut-Hetep (circa 1650 B.C.), there is a description of how olive oil was applied to wooden planks so that heavy stones might be moved more easily. Plinius (23–79 A.D.) compiled a list of lubricants made from plants and animals that were well known at that time and are still used today. Bearings and slow-moving machinery were lubricated from antiquity up to the beginning of the nineteenth century with oils made from olives, rape seed, castor plant seeds, and other naturally occurring friction reducers. These were the first lubricants.

The Second World War provided the primary stimulus for the development and use of synthetic lubricants. During this time, nations faced a real possibility of running short of crude oil. This challenged America’s oil companies to seek ways of manufacturing lubricants and fuels from natural gas and other noncrude resources. Additionally, new devices, such as jet engines, came into being, creating new performance criteria especially in terms of high-temperature degradation resistance. Existing equipment during the war was exposed to environmental extremes—arctic and subarctic regions, for example—that led to requirements that mineral lubricants could not fulfill.

Such demands during World War II resulted in the first truly commercial use of synthetic lubricants. These are defined as products made from base fluids manufactured by chemical synthesis. Polyalkylene glycols (polyglycols) were used for lubrication in the military for the first time in 1940, although these substances had been known for about a hundred years. They were used more extensively in industry after 1945, with the end of military secrecy. Today, polyglycols are well known for use as brake fluids, high-temperature lubricants, and energy-efficient oils for gearboxes (Mobil Oil Corporation, 1999).

The chemical history of o-phosphoric acid esters is as old as that of polyglycols. Triphenyl phosphate was synthesized for the first time in 1854. Phosphoric acid esters attracted industrial attention for the first time around 1920 as softening agents for cellulose nitrate. In recent years, tertiary phosphoric acid esters have been further developed as defoamants, wear-resistant additives, and especially as fire-resistant hydraulic fluids.

Although research work on dibasic acid esters began long before, these materials—in their various chemical forms—assumed an important role as lubricants with the advent of World War II. On both sides of the conflict, researchers were working to develop new lubricants and fluids that would be less sensitive to temperature change—i.e., remaining more fluid at very low temperatures, and being less volatile and more stable at very high temperatures. A great deal of this effort centered on dibasic acid esters, resulting in a variety of specialty products for instruments, fire control apparatus, gyroscopes, and special aviation and naval ordnance equipment. Simple esters, although used as lubricants in early jet engines, lacked thermal stability, which limited flight time between engine overhauls to only a few hundred hours. In Germany, esters were used as automotive engine lubricants. In the early 1950s, British and U.S. researchers produced diester oils for the engines of jet aircraft, first for the military and then for commercial uses including engine oil and industrial applications. More recently, polyol esters have replaced diesters in many jet applications an...