Search Documents

By G. C. RIDDELL

THE metallurgist, chemist, and physicist are blazing trails that lead far afield. Pushing on into an "Alloy Age" they see a non-ferrous era over- taking iron and steel. Delving into the nature of the physical world, they break down a supposedly indivisible element, hydrogen. Not content with terrestrial problems, they peer back along the cosmic ray into iaterstellar space, glimpsing forces that are, apparently, still busy with the task of atom-making. Mastering and organizing the material and physical, they advance steadily toward that borderland of science where the concept of matter itself seems abandoned, and force is the substance left.

Jan 1, 1930

By W. F. Dietrich

Mineral fillers are relatively inert chemically under the conditions of use but have physical properties* that modify those of the materials • The properties. uses, and other data on 15 classes of important *The pro listed in the second edition of Industrial Minerals and Rocks.l A third edition of this reference is in preparation. in which they are incorporated. The mineral fillers considered in this article are asbestos, barite, clays, diatomite, crushed limestone, limestone whiting and lime, mica, silica, talc and soapstone, and pyrophyllite. Slate and stone, other than limestone and its derivatives, are excluded because, even though used in large quantities, they are exceptionally low-cost materials generally produced close to the area where they are used. Carbon black is excluded because it is manufactured from natural gas and more than 90 pct of the output is used in rubber; hence the factors for estimating requirements are easily evaluated. OVERALL GROWTH FACTORS Table I gives the population, retail sales, and value added by manufactures in the U. S. and in the eleven western states in 1954. These data are rough guides to the proportionate part of total U. S. markets for products containing mineral fillers that may be expected in a given area. For example, the population of the eight Mountain states in 1954 was 3.6 pct, and retail sales in these states were 3.8 pct of the U. S. total, but the value added by manufactures was only 1.3 pct of the U. S. total. On the other hand, the three Pacific Coast states, with 10.3 pct of the total population, had 12.0 pct of the retail sales and produced 9.6 pct of the value added by manufactures. On an industry-by-industry basis the correlation between the three guideposts will not be as close as shown in the 1954 data for the Pacific Coast states, but in the long-term view the continuing rapid population growth in the western states is certain to result in expanded industrial production at an even more accelerated pace, which will shorten the gap between local consumption and production in most major groups of manufactured consumer goods. Of course, there will always remain favorable areas for production of specific products. Such special situations must be individually analyzed. Fig. 1 compares the population trends in the U. S., the western states, and California with Real Gross National Product from 1910 to 1957, with forecasts to 1970. It is estimated' that the U. S. Real Gross National Product, as measured by the value of goods and

Jan 1, 1960

By W. W. Fowler

ORIGINALLY designed for copper smelting only, the reduction works of the Cerro de Pasco Copper Corp. have been expanded over the years until now twelve different metals are produced, together with some seven other items which are used locally. Although the total tonnage treated is comparatively modest, as smelting plants go, the variety of operations makes one of the most complex and interesting metallurgical problems in the world. The original plant, at La Fundicion, operated from July 1906 until September 1923. In 1922 a new copper smelter was built at La Oroya, which produced its first copper on Nov. 23, 1922. It is in this plant, greatly enlarged, that metallurgical operations now center. La Oroya is situated at the junction of the Cerro de Pasco Railroad and the Ferrocarril Central del Peru, at an altitude of 12,175 ft.-well over two miles. Many of the various operations stem from two principal smelting circuits which are themselves of conventional types. Copper ores and concentrates are roasted, smelted in reverberatory furnaces and converters, and blister copper produced. Lead ores, concentrates, and other materials are sintered, smelted in blast furnaces to crude lead which is partially fire-refined, and finally electrolytically refined by a modified Betts process.

Jan 1, 1945

By Arthur Forsyth

A SEARCH through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1.

Jan 1, 1940

By Cyril Stanley Smith

Although alloys of copper and silicon were examined several years ago,' and their excellent mechanical properties were shown, it was not until C. B. Jacobs 2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. Review of Previous WORK on the BinaRy Systems There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described," which indicate that there is a change in solubility with temperature. Copper-silicon System The copper-silicon system has been studied in detail by the author and is described in two papers published in 1928.V he portion of the diagram up to 8 per cent. silicon, as determined by this research, is reproduced in Fig. 1. The author's previous papers include a complete review of the work of other investigators and it is not necessary to deal further with this system here. Copper-manganese System The copper-manganese system has been investigated by several workers, notably Lewis,5 Wologdine,6 Sahmen7 and Schemtschuschny,

Jan 1, 1930

By J. D. Doherty

That America's great coal deposits eventually will be our principal source of liquid as well as solid fuels is generally accepted. Moreover, the day when synthetic oil from coal will begin to supplement our petroleum supplies does not appear to be far off. The American petroleum industry has not spared effort or expenditure in its attempt to keep pace with the demand for oil, and recent production has exceeded expectations. However, the rapidly rising demand for liquid fuels plus the increasing difficulty of finding and developing the new oil needed even to maintain present production rates make it highly unlikely that oil from domestic wells can fully meet future oil requirements. Therefore, it appears that one or more of the following courses must be followed: 1. Curtail oil consumption. 2. Increase imports. 3. Develop new sources such as synthetic liquid fuels.

Jan 1, 1949

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By William G. [Peryam], Bishop Ottey M., Fred E. Johnson

THE Lepanto Consolidated Mining Company is the largest copper producer in the Philippines, and the only one that makes a concentrate valuable principally for its copper; also, it has the only productive copper mine situated at considerable distance from the sea, and is the only one in the islands operating its own smelter. The Lepanto mine is in the Municipal District of Mankayan, sub-province of Benguet, near the heart of the Mountain Province of Northern Luzon. It is 165 km. from its shipping point at San Fernando, Province of La Union, on the shore of the China Sea. Elevations at the property range from 3200 to 4500 ft. The climate is very mild; temperatures are seldom below 50° or above 80°F. Annual rainfall approaches 170 in. and is mainly confined to a rainy season lasting from May to October. The months from December to April, inclusive, are usually extremely dry. This climatic pecularity entails the problems of landslides on the roads during the rainy season and water shortage during the dry season. The Mountain Trail, an improved rock-surfaced toll road maintained by the Commonwealth Government, gives access to the property. The 105 km. over this road may be traveled in about 4 ½ hr. during the dry season. Very few sections of the road are straight for more than 100 meters, and about one third of it is a one-way road controlled by gates. All freight for the property is delivered by the Manila Railroad Company to Bauang, La Union, 45 km. west of Baguio and at sea level, where it is picked up by freight trucks and hauled via Baguio to Lepanto. Granulated matte is hauled in bulk from Lepanto in four-ton lots on freight trucks to the storage bins at San Fernando. Freight rates from Bauang to the property amount to P8.00 per ton, and from the property to San Fernando the rate is P16.00 per ton. The company pays the road toll, P1.00 per truck, each way. THE CAMP The company maintains a modern camp, well separated from the mine and reduction plant. Comfortable and sanitary living quarters, water, and light, as well as free medical service are provided all employees. A hospital staffed by a doctor and two nurses takes care of all medical treatment. Considering recreational facilities of great importance, the company has provided two tennis courts, two basketball courts, and badminton courts for employees. Bowling alleys and a motion picture theater are operated by the company, the profits being expended for other recreational purposes. A moderate sized recreation hall serves for barrio dances, meetings,

Jan 1, 1942

By J. E. Tobey

NATIONAL DEFENSE should not create a dilemma in coal utilization such as obtained during the World War. Even under the heavy pressure of a total preparedness program there should be a smooth flow of the right coals from mines to plants. The more than 100,000 industrial plants of the nation must he served with coal of such characteristics and qualities for their individual requirements that no loss of production due to coal failure shall occur. This problem challenges the ingenuity and cooperativeness of producers. transportation executives, consumers and engineers.

Jan 1, 1941

By Frederick Rhines

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ? in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activa-tion heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. Much of the argument concerning the properties of metals that deter-mine D and Q has been drawn from data in which variations of the quan-tities with concentration are unknown, for these data- have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concen-trations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

In response to Dr. Ledoux's paper, a large number of metallurgical establishments and individual assayers expressed their willingness to co-operate in the plan he proposed. The necessary samples were prepared as follows : Matte.—A car-load of matte was put through a Blake crusher, then automatically subdivided into tenths by a Taylor and Brunton sampler, and one-tenth passed through Cornish rolls and through a 12-mesh screen. This was again subdivided by an automatic sampler into tenths, and a final tenth, representing 1 per cent. of the original lot, was finished by hand-sampling on an iron floor until 100 pounds remained. This was pulverized to pass a 40-mesh screen and then thoroughly mixed and divided in the presence of my assistant for distribution to the parties co-operating. Copper Borings.—These were taken from a lot of anodes, the dip-samples from several batches having been united, remelted and cast into a plate, which was proved by assay to be of uniform quality in its different parts. Borings from this plate were intimately mixed and divided in the presence of my assistant. Samples were sent out November 1,1894, with the following letter: New York City, November 1, 1894. Samples of matte and copper (about I pound each) carefully prepared in the presence of my assistant and sealed with his seal as below, are sent you by express for assay and report according to the plan of Dr. Ledoux. These samples are constituted about as follows: Matte. Copper. From. To. From. To. Copper, per cent.,.....50 60 ..........., Gold, oz. per ton,.....2 3 0.20 0.50 Silver, oz. per ton,.....100 150 140 180

Jan 1, 1896

By F. L. Bosqui, A. D. Wilkinson

EVEN though the world has not been crying for more copper for the last three or four years there has been some important mill and smelter construction. Discovery and development of large new high-grade copper deposits in Africa has led to the construction of extensive reduction facilities there, prominent among which is the concentrator and smelter of the Rhokana Corporation at N'Kana. Northern Rhodesia. The 3000-ton concentrator adjoins the central shaft. A little over half a mile to the southeast, at an altitude of 40,010 ft., is the smelter, designed on the site by 1. H. Wynne. It is arranged primarily to treat N'Kana copper concentrates, but can also handle concentrates and direct-smelting ore from outside sources. Excavations were started late in 1930; concrete was first poured on Jan. 6. 1931; and the first blister cop¬per was cast on March 1.9, 1932, less than fifteen months later. During this period, which included several months of heavy tropical rains, some 10,000 cu. yd. of concrete was poured and 41000 tons of structural steel erected under the supervision of construction engineer, A. Ek, with a labor force of 60 to 30 Europeans and about 300 natives. The steelwork was fabricated by Head Wrightson & Co. in England, and the boiler plant equipment furnished and erected by the International Combustion Co. Ltd.

Jan 1, 1934

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

By Bieniawski, Z. T.

The importance of understanding the phenomena associated with rock fracture has long been fully appreciated in rock mechanics. This is clearly apparent from the special attention paid to rock fracture in the comprehensive papers published within the past four years. These papers present a picture of how the knowledge of brittle fracture of rock was gradually enriched and also show that what was often taken for granted three or four years ago is no longer considered as valid today.

Jan 1, 1972

By R. H. Richman

Coarse-grained Fe-Ni-C martensites formed at subzero temperatures were strained in compression at room temperature and the plastic deformation modes examined as a funclion of carbon content. At very low carbon levels, defovmation occurs hy wavy slip; commencing at about 0.05 pct C, mechanical twinning accounts for an increasing proportion of the plastic flow. Beyond approximately 0.4 pct C the deformation appears to be entirely by mechanical twinning. The habit planes of the operative twin modes were determined to be (113), (0131, and "(089)" in decreasing frequency of occurrence. Some of the implicaticms of Ihe o6served deformation modes upon the structure and properties of ferrous martensites are discussed. METALLURGISTS have long sought to explain the mechanical properties of ferrous martensites, particularly the extraordinary hardness and strength of the high-carbon varieties. Until recently the lack of precise knowledge of the structure of martensite crystals was the most serious barrier to understanding; however, the advent of thin-foil techniques for transmission electron microscopy has removed much of the mystery from martensite structure. Observations by Kelly and Nutting,"' and many others since, indicate that Fe-C based martensite crystals are internally twinned to a degree dependent upon the carbon content, and that a martensite plate containing 0.8 wt pct C or more consists of a stack of twin-related lamellae with each lamella on the order of l00A thick. Such a structure would be expected to influence greatly all aspects of metallurgical behavior, and many of the properties of Fe-C based martensites have been rationalized accordingly. Recent independent experiments led Winchell and cohen3 to conclude that the strength of ferrous martensite is derived primarily from solid solution hardening of the iron lattice by interstitial carbon atoms. Strength contributions from precipitation, dislocation-atmosphere interactions, clustering, short-range order, crystallite size, and so forth, were considered to be of secondary importance. In the view of Winchell and Cohen, the twinned structure of martensite serves mainly to limit the effective length of dislocation lines in the lattice, and thereby confers an added measure of hardening. Few properties of metallic crystals are as sensitive to metallurgical structure as are deformation mechanisms. It is somewhat surprising therefore, that, except for metallographic evidence of mechanical twins in strained martensite,4 no systematic examination of plastic deformation

Jan 1, 1963

Receipts, Jan. 1, 1914, to Dec. 31, 1914 Cash on hand, Jan, 1 1914 General Funds $1,843.54 Special Funds 1,039.00 $2,882.54 Initiation Fees $8,500.00 Annual Dues 44,060.84 Life Memberships 1,950.00 54,510.84 Sale of Transactions 4,798.87 Sale of Binding 10,029.06 Sale of Bulletins and Pamphlets 2,508.25 Sale of Special Editions 1,290.74 Sale of Advertising 8,783.29 Sale of Library Books 54.97 Sale of Pins and Fobs 347.65 Miscellaneous Sales 21.66 Space Released 5,943.00 Interest on Investments and Bank Deposits 230.15 34,016.64

Jan 1, 1917

By N. O. Taylor

THE failure, by swelling, of several cast aluminum-zinc, spiral, pump rods, used to circulate water in a constant-temperature bath, brought up the question as to whether the presence of tin in varying quantities would have any appreciable influence in controlling this action. Previous workers had found the same difficulty with aluminum-zinc alloys, due to their swelling in water or solutions of electrolyte^.^ It was known that pure aluminum was practically insoluble in concentrated sulfuric and nitric acids, presumably due to the formation of an oxidized film on the surface. Concentrated sulfuric acid had little or no effect on pure zinc and tin and concentrated hydrochloric acid would attack all three metals. These facts aroused curiosity as to the probable reaction of the ternary alloys of these metals, and tests were made to determine their resistivity to the action of common laboratory reagents. Samples, covering the entire range of the ternary series of aluminum, zinc and tin alloys, were made up from good grades of the commercial metals.2 The materials were melted, at as low temperatures as possible, in graphite crucibles in a gas-fired crucible furnace. Graphite crucibles were used in preference to clay, to prevent the absorption of silicon by the aluminum, as found by previous workers. The melted materials were stirred thoroughly with pine sticks in order to ensure complete mixing and the greatest possible freedom from oxidation, and were cast in sectional, iron molds giving bars % in. in diameter and 5 in. long.

Jan 1, 1927

By Everett D. Jackson

The largest deposits of chromite in the United States occur in tabular layers in the lower part of the Stillwater Complex, Montana. Nearly 900,000 long tons of chromite concentrates have been produced from mines and mills in this area, and reserves equivalent to more than 2,500,000 long tons of Cr2O3 remain in the ground. Layered concentrations of chromite (known as chromitite zones) occur only within olivine-rich layers of the Peridotite member of the Ultramafic zone of the Stillwater. As many as thirteen chromitite zones, lying conformably one above another, have been found, but only five of them are thick enough to be of any conceivable economic interest, and only two of them have been mined to date. Individual chromitite zones can be recognized by their distinctive internal character and by their stratigraphic position in the Peridotite member. The chemical composition of chromite varies consistently between and within the different chromitite zones. The zones range in thickness from about an inch to more than 12 feet, and the Cr2O3, content of their chromite ranges from 36.6 to 49.2 weight per cent. In any given area, the G chromitite zone is the thickest, but the chromite of the H chromitite zone has the highest grade. Laterally, the thickness of the chromitite zones is related to the thickness of the Peridotite member; in general all are thicker in the eastern part of the Stillwater than in the western part.

Jan 1, 1968

By M. E. Lombardi

THE Coalinga oil field is located on the west side of the San Joaquin Valley, California. The structure is in general a monocline, the edges of the oil horizon resting on the foot hills and dipping gently toward the east. One prominent anticline occurs plunging southeast. The earlier drilling was done in the foot hills comparatively near the outcrop and the wells were shallow. The sands were followed eastward and, in the case of the anticline, along the plunge, the wells becoming deeper and deeper until the depth of 4,000 ft. was reached and passed. There is nothing to show that the oil will not be found in quantity at still greater depth. In fact, some of the best producers have tapped the sand at close to 4,000 ft. The recovery of oil still farther to the east, and therefore at greater depth, seems to be mainly a question of drilling. In this territory the formations drilled through are chiefly sands and shales; they will not "stand up" in an open drilling hole; the casing has to be carried close to the bit, and it is always difficult to keep the casing free for any considerable distance. Ability to carry casing of comparatively large diameter without conductor pipes for distances of 2,000 or 3,000 ft. or over is desirable in such territory chiefly for two reasons. It makes it possible to enter the oil sand with a pipe of ample diameter; it eliminates one or more expensive strings of casing which act only as conductors for the water string, and furthermore, in territory where waters are encountered which corrode steel rapidly, it makes possible the construction of a rust- and alkali-resisting water string. It is always desirable to shut off top waters, which may lie within 100 ft. or less of the oil sand, with 10-in. pipe. Where the depth is so great that a practical weight of 10-in. pipe will not withstand the probable collapsing pressures, 8 ¼ in. at least is desirable. About the limit of rotary drilling to date in California seems to be the setting of the 10-in. string at 3,200 ft., although the rapid advance in rotary work during the past year seems to indicate that this depth may soon be increased. It is my purpose now, however, to treat only of cable-tool drilling.

Jan 2, 1915

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970