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By Darwin Soler

This chapter will outline the operating procedures at Freeport Kaolin Co.5 kaolin mining operations in Georgia, with emphasis on explaining new techniques recently introduced to reclaim mined-out areas for reforestation. Kaolin is found in the central Georgia area (See Fig. 1) in lenticular, sedimentary deposits of high purity. The beds are Cretaceous in age and vary from 4 to 60 ft in thickness, under a cover of sedimentary overburden ranging from 5 to 150 ft. The kaolin beds contain the mineral kaolinite (a hydrous aluminum silicate) and have a particle-size distribution ranging from about 20µ to the submicron level and averaging about 60% below 2µ. The only contaminants in the deposits are coarse mica, quartz particles, and minor amounts of iron and titanium oxides. These kaolin deposits vary widely in quality from deposit to deposit and also vary within individual deposits. Some of the controlling quality specifications which are determined during exploration are viscosity in water suspension, optical brightness index as measured by reflectance, amenability to bleaching, and particle-size distribution. For this reason, only a small portion of the total kaolin reserves in the Georgia belt are suitable for wet processing for the present markets being served. Kaolin clays are selectively mined by different mechanical methods and are beneficiated by both wet and dry processing to produce a number of products used as fillers and coatings in the paper industry; fillers or additives in the paint, plastic, and rubber industries; and as basic raw materials for the ceramic industry. The State of Georgia is the largest kaolin producer in the United States, with 3,206,454 tons produced in 1966, according to U.S. Bureau of Mines statistics. Freeport Kaolin Co’s processing plant is located in Gordon, Ga., about 20 miles east of Macon, Ga.

Jan 1, 1969

By R. T. Mishler

I WISH to express my keen appreciation of the article on the above subject by Coe and Clevenger.1 It has been doubly interesting to me, for the reason that the experience recorded and the principles evolved practically parallel the results of similar investigations made by myself and others at The Lucky Tiger Mine, El Tigre, Sonora, Mex. An outline of the work at El Tigre may aid in confirming the principles expressed by Coe and Clevenger. El Tigre has the unenviable distinction of possessing a slime with a much lower settling rate than any recorded in the article discussed. Under most favorable conditions the settling rate is about one-third that reported for the Liberty Bell mill, and one-tenth that reported for the Nipissing, Golden Cycle, and Presidio mills. This slow settling characteristic of Tigre ore has necessitated careful investigation of settling phenomena throughout the various evolutions of the plant. PREVIOUS SETTLING INVESTIGATION AT TIGRE During construction work at the mill, the Metallurgical Engineer in charge, D. L. H. Forbes, ran a series of experiments on settling. His tests proved that deep settling tanks were not ordinarily necessary. The use of tanks 2 or 3 ft. in depth was suggested.2 Later experiments demonstrated that the following principles of settling applied to Tigre pulp.3 1. In settling dilute pulp, settling rates are independent of pulp depth. 2. In settling thick pulp, settling rates are approximately proportional to pulp depth.4

Jan 3, 1917

By William L. Fink, H. R. Freche

This is the thirteenth paper of a series from the laboratories of the Aluminurrl Company of America presenting the results of investigations of equilibrium relations in aluminum-base alloys prepared from electro-lytically refined aluminum. The ninth paper, on The Constitution of High-purity Aluminum-titanium Alloys,' presented a type of system that had not previously been encountered in aluminum alloys. Subsequent work has shown that there are several similar binary aluminum diagrams including that of aluminum and chromium. The present investigation was limited to the cxtreme alnminum end of the aluminum-chromium system. The first systematic investigation of the aluminum-chromium equilibrium diagram was carried out by Hindrichs.? The resulting equilibrium diagram with some imaginary additions suggested by Guillet3 is shown in Fig. 1. Recently Goto and D6gane4 investigated the constitution of aluminum alloys containing up to 32 per cent chromium, and presented the diagram that is reproduced in Fig. 2. Wide discrepancies in the two diagrams are evident. The following intermetallic compounds have been reported in the literature: A1Crl5,6 AlloCrlzSi,5 AlCr4,6 AlCr3,7 AlaCr.8 Preparation of Alloys and Chemical Analyses With the exception of sample Y4206, which will be described under Determination of Hyperperitectic Liquidus, the alloys were prepared from electrolytically refined alurninum% Of which the analysis is given in

Jan 1, 1933

By Ovid W. Eshbach

ENGINEERING education has been powerfully affected by the impact of war, just how powerfully can be better understood after considering the postwar problems regarding students, staff, and plant. In time of war no one will question the necessity of expediency of military training. With the cessation of hostilities, expediency gives way to the evolutionary process of strengthening engineering education as need is exemplified by experience. During the war, except for the Navy V-12 program, engineering education was at its lowest ebb of the century. Freshman enrollments were largely limited to those graduating from high school at the age of seventeen; and the upperclass, to those disqualified for active service. In most schools the experienced staff was either in service or government and industrial research. Many may never return to their former occupations. The most immediate problem is that of maintaining and building a staff to meet the enrollment of returning veterans. It is estimated that out of the eleven

Jan 1, 1945

By Allen D. Gorrison

EFFORT to develop fundamental quantitative information and improved technique in the production of petroleum has long been faced with difficulties of a particularly evasive nature, owing to a combination of circumstances. In the first place, petroleum comes from far below the ground, out of sight, so that information derived from indirect observations must be extrapolated to reservoir conditions. If one does not force the analogy too far, the petroleum engineer may be said to be somewhat in the position of the astronomer. The actual phenomena which he wishes to observe in detail appear at a place so deep in the earth?s crust that personal observations and direct experiments are impossible.

Jan 1, 1942

By C.F. Pascoe, H.J. Roast

The object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4.Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests.' 8. Brinell tests, at temperatures from 80' to 400' F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: Lead. ' Antimony, Tin, CoppeR ARSEnic, NumBeR PeR CENT. PER CENT. PeR Cent. PeR CeNt. PeR Cent. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.04 59.87 2.65 none I 3 none- 0.13 ------------1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 . 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sul-furic acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thio-cyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference. With the exception of No. 5, the alloys were taken as received from the manufacturer. About 40 lb, were melted in a graphite crucible and recast into small ingots to insure uniformity of composition; samples

Jan 1, 1923

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By George A. Morrison

The Columbia Chemical Division of the Pittsburgh Plate Glass Co. is at Bar-berton, Ohio, 35 miles south of Cleveland. For many years large tonnages of limestone have been brought to the Barberton plant from distant points. The stone is here burnt in vertical kilns, the resultant product then hydrated and the hydrated lime used in chemical processing. To eliminate the expense of these shipments, the company decided to investigate a limestone bed known to exist on company property at Barberton, where the stone is used. The bed lay at a depth of more than 2000 ft. and was known locally as the "Deep Lime." Chemical analyses of sludge from churn-drill holes made some years ago proved that the limestone was of sufficient purity to warrant diamond-drill exploration. Four diamond-drill holes were put down at well-spaced intervals, to represent fairly an area of four miles by one mile. Cores logged as to chemical and physical conditions were found to compare closely, and to corroborate the earlier evidence that the limestone was of superior quality for chemical use. A plant of 300 tons per hour was subsequently decided upon. SITe The yard at the chemical plant was already so congested that location of the projected mine within its area could not be considered. Eventually a site was selected 2 miles northwest of the plant, near the main line of the Erie Railroad. Here 412 acres were owned outright by the company and stone rights were obtained on 2 50 additional acres. This location required a transportation line of nearly 2 miles (8800 ft.), crossing two major highways, and to avoid interruption of deliveries to the plant, overpasses were planned. Geology The limestone in the immediate vicinity lies about 2200 ft. below the surface. Geologists* identify this stone as Delaware of Devonian age. It is overlain by 18 ft. of unconsolidated (sand and gravel), 100 ft. of water-bearing sandstone, and finally 2080 ft. of shale into which sandstone in thin layers is interbedded. The contact of shale and limestone is abrupt, flat-lying and very pronounced. Berea sandstone, often found at 520 ft., is absent, but Euclid sandstone was encountered, together with a seepage of oil and a small amount of methane gas. The limestone bed itself is 345 ft. thick, and overlies 200 ft. of gypsum. The lower part becomes dolomitic as it approaches the gypsum. A detailed study of the drill cores indicates that the upper 50 ft. are highest in lime and reasonably low in silica. The physical make-up shows several separating cherty layers. These occur at definite horizons and cause distinct partings, which become horizontal planes of

Jan 1, 1946

By Hubert D. Keiser

AN observation that is finding fresh confirmation in the leadership of the Allied Nations is "When the need arises, a man will rise to fill it." Much the same can be said of industrial advances in the current emergency. Events and circumstances have created needs for new materials and stimulated the inventive genius of man to fill them. The timely development of fibrous-glass manufacture, in relation to present war needs, is a case in point. HISTORICAL SUMMARY It is probable that the first glass fibers produced by the hand of man were made about 4000 years ago. Successful production of glass fibers for manifold industrial and military uses, on any scale that could begin to meet present needs, has a history spanning a scant four years. The American processes that brought this young industry into being were developed between the years 1931 and 1937; research and manufacturing efforts were consolidated to create a commercially satisfactory operation as late as November 1939. In the 40 months that have elapsed since then, the industry has achieved commercial importance, supplied immense quantities of materials for pre-war industrial expansion to meet "defense" and Lend-Lease needs, and now has reached such importance that it has come largely under the control of the War Production Board for equitable distribution of its major products among 13 claimant agencies. It is worthy of note, however, that the Bureau of Ships, Navy Department, began exploratory use of fibrous-glass products in 1932, within one year after the date of the first experimental trials of the new process. This early recognition of the military importance of fibrous glass gave impetus to further research work. The foregoing rapid scanning of historical development must be filled in, lest the impression be created that glass fibers were suddenly created out of thin air, with no antecedent trials, failures, and partial successes. The actual history of glassmaking is lost in antiquity. Probably some nomadic tribesman found molten glass beneath the bed of a hot campfire built upon sand of the proper composition. If his curiosity led him to poke the glowing, viscous pool with a green-wood stick or some handy weapon, it is probable that he drew a glass fiber on the end of his implement. Molten glass has much the same consistency as honey or molasses; it strings out tenuously. Thus, it is quite possible that the first form of glass shaped by man's action was a glass fiber. Artisans in glass, throughout the long history of glassmaking as an art, drew fibers from fine rods for many decorative applications, including "spun glass" decoration in beautiful stemware and the charming millefiori (glass flowers encased in solid glass), and even to create the blood vessels in glass eyes to match a bleary mate.

Jan 1, 1943

By R. L. Bleifuss

Most pellets swell only slightly during reduction, but some swell so enormusly that their increase in size is termed catastrophic. Since catastrophic swelling produces irregularities in blast furnace operation, an understanding of the phenomenon is of practical as well as theoretical interest. Observations have shown that catastrophic swelling is characterized by the growth of a network of fine iron filaments. Evidence is presented to show that the growth of these filaments is promoted by the presence of calcium in the magnetite lattice of the original ore. During reduction, the limited mutual solubility of CaO and FeO produces an unstable condition that inhibits the uniform nucleation of metallic iron. Other elements in the magnetite lattice whose oxides are continuously soluble in FeO in the critical temperature range have no effect. Magmatic segregation or pyrometasomatic replacements are the most likely deposits to contain calciferous magnetite. Over the past few years there has been an increasing concern throughout the iron and steel industry over the tendency of pellets to swell during reduction. Although the tendency for swelling is only one of several attributes that determine the behavior of pellets in the blast furnace, swelling-reduction tests are now part of the normal evaluation procedure of many pellet consumers. During a swelling-reduction test, pellets display either the moderate increase in size known as normal swelling, or the enormous expansion known as catastrophic swelling. This paper is concerned with the origin and control of catastrophic swelling and how it is enhanced or inhibited by the presence of minor elements. Swelling Behavior The swelling behavior of pellets during reduction is indicated in Fig. 1. The lower curve represents normal swelling and the upper curve catastrophic swelling.' During the initial stages of reduction, that is, up to about 20-25% reduction, the two curves are considered to be equivalent. Beyond this point normal pellets undergo a gradual decrease in size with increased reduction. By contrast, pellets which exhibit catastrophic swelling show a second dramatic expansion between 25 and 70% reduction. The initial normal swelling develops as the hematite of the pellet is successively reduced to magnetite, and then to wustite. Work by Edstrom' and others has shown that the reduction of hematite to magnetite is accompanied by a 25% volume increase, whereas the magnetite to wustite stage shows a volume decrease. The volume increase overlaps the wustite field because magnetite is formed simultaneously with the wustite during topochemical reduction of the pellet. The catastrophic expansion is clearly related to the wustite, to

Jan 1, 1971

For many years it has been known that large bodies of iron ore existed in Iron and Washington counties in Utah. The ore is chiefly hematite-both hard and soft-though some magnetite is found. No definite and complete estimate of the iron ore reserves of the state have been made. The U. S. Geological Survey estimated that 40,000,000 tons of ore were disclosed by development work averaging only 35 feet below the surface of the ore. The ore is found along an area about one and a half miles wide by twenty miles long, and for the most part on the eastern and southern slopes or foothills of Three Peaks. Granite Mountain and Iron Mountain. Later estimates by others have gone as high as ore in sight 164,000,000 tons, probable ore 300,000,000 tons and possible ore 1,000,000,000 tons. Whether this last estimate is too great or not there is sufficient iron ore in Utah to justify the starting of an iron industry. Two companies are now mining iron ore in Utah, the Columbia Steel Corporation and the Utah Iron Corporation. The mine of the Columbia Steel Corporation is at Iron Springs a few miles west of Cedar City. About 650 tons, of ore a day is being shipped to the blast furnace at Ironton. The ore is mined by the glory hole method. After being drilled it is blasted to the bottom of the several glory holes and is dropped through chutes into cars on the ore haulage level below. It is then hauled by electric locomotives to the crushing plant, where it is crushed to blast furnace size before going to storage bins. Some of the softer ore is brought to the chutes by Fresno scrapers.

Jan 1, 1925

By C. F. Pascoe, H. J. Roast

The object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4.Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests.' 8. Brinell tests, at temperatures from 80' to 400' F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: Lead. ' Antimony, Tin, CoppeR ARSEnic, NumBeR PeR CENT. PER CENT. PeR Cent. PeR CeNt. PeR Cent. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.04 59.87 2.65 none I 3 none- 0.13 ------------1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 . 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sul-furic acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thio-cyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference. With the exception of No. 5, the alloys were taken as received from the manufacturer. About 40 lb, were melted in a graphite crucible and recast into small ingots to insure uniformity of composition; samples

Jan 1, 1923

By William H. Case

The Bertha zinc-mines of the Bertha Zinc and Mineral Company are in that part of the State of Virginia popularly known as Southwest Virginia, and are included in that division of the " Great Valley " named in recent years the " New River-Cripple Creek Mineral-Region of Virginia." The mines lie wholly in the southeast part of Wythe county, two miles from Pulaski county on the east, and three miles from Carroll county on the south. The only other zinc-mines that are opened in the region are those of Manning & Squier, which adjoin the Bertha zinc-mines on the northeast, and the mines of the Wythe Lend and Zinc Company, at Austinville, eight miles to the southwest. A little farther southwest of Austinville, near Ivanhoe, a new company is preparing to mine zinc-ores. The mining properties named are included within a distance of ten miles along a direct line, bearing north 55' east, on the south side of New river, which here flows northeastward in a tortuous course. The greatest distance of any of the mine-openings from the river is a little less than two miles. It is not the magnitude of the operations in zinc-mining in this particular region, as compared with that of other well-known districts, that merits especial notice. Aside from the exceptional purity of the spelter made directly from the Bertha ores, some peculiar features of the zinc-ore deposih, as shown at the Bertha mines, and

Jan 1, 1894

By Reno H. Sales

Jan 1, 1914

By Tom Westgarth

As papers are placed before you upon large gas-engines in Belgium and Germany, it was considered that some information should be given upon the same subject in Great Britain. I therefore agreed to compile these notes, which I have made very short in view of the somewhat full nature of the other papers presented to this meeting, and considering the complete nature of the many publications which have been made recently upon the subject of large gas-engines. I give below Tables I. to VI., showing the number and particulars of large gas-engines which have been built or are building by British makers, and in view of the growing size of gas-engines I have concluded that engines less than 500 h.p. cannot now be included in the category of large gas-engines, and therefore I have not considered engines under that power.

Nov 1, 1906

Readers of recent Bulletins have doubtless observed that the problem of improving both material and moral condition of employees is receiving close attention from influential members of the Institute. This will lend interest to certain developments and investigations that have been reported elsewhere.

Jan 5, 1918

By S. W. Kennedy, M. Cohen, L. D. Calvert

A high-temperature X-ray diffraction method has been used to study the composition and the kinetics of formation of oxide scales at 800 °C on iron and pure iron-nickel alloys containing 25.6, 75, and 84 pct Ni. This technique has been combined with chemical analysis, and metallographic examination, and determination of weight-gain time curves. The 75 and 84 pct Ni alloys form a three-layer scale consisting of porous NiO next to the metal, a spinel layer, and a -Fe203 on the outside. The 25 pct Ni alloy produces a scale of spinel and Fe,O,, in which, however, traces of FeO and NiO are observed near to the metal. On all the nickel alloys the Fe20, is orieqted with the (107) plane parallel to the surfaces. The exposed surface of the Fe20, is in the form of needles whose axis is perpendicular to the specimen surface. Although the alloys show nonuniform oxidation rates as determined from weight-gain measurements, the X-ray data indicate that the total scale and individml scale layers grow uniformly and parabolically. Deep subscale formation is observed in the 25 pct Ni alloy only. This appeared to be associated with cracking of the scale and penetration of the oxygen along the grain boundaries. ALTHOUGH film formation has been investigated by high-temperature electron-diffraction techniques, for example by Gulbransenl and Hickman,' there have apparently been no investigations of scaling by methods permitting study of the scale during formation at the reaction temperature. Methods involving quenching of scales are based on the working assumption that no significant changes take place on cooling. In general, however, compounds may disproportionate, and the different thermal expansions of constituents may cause disruption of the scale on cooling. In particular, some scales cannot be quenched without spalling. These difficulties are avoided by X-ray diffraction examination at the temperature of formation. High-temperature diffraction procedures also provide a method of determining the kinetics of formation of each phase separately in a multicom-ponent scale. The scaling of binary iron-nickel alloys Containing up to 30 pct Ni at a temperature of 800°C has been studied by Benard and Moreau using cooled specimen~,~ whilst Foley, Druck, and Fryxel14 made an electron-diffraction study of cooled oxide films formed on an iron 42 pci Ni alloy. In the present work the scaling of three iron-nickel alloys containing 25.6, 75, and 84 pct by weight of nickel, at 800°C in oxygen at atmospheric pressure was investigated by X-ray diffraction techniques using a Norelco Geiger-counter diffrac-tometer. The oxidation of iron was investigated for comparison. In addition normal metallographic examinations and chemical and X-ray analyses were made, and weight-gain time curves obtained. EXPERIMENTAL Materials Used—The analyses of the alloys were as follows: Percent by Weight Nickel 25.6 pct 75.4 pct 83.2 pct Aluminum 0.004 None found 0.002 Cobalt — 0.05 0.05 Chromium — — — Silicon — 0.01 None found Carbon All less than 0.05 pct The chemical analysis of the iron was: Al— 0.002 i 0.001 pct, C—0.007 pct, Cr less than 0.001 pct, Cu—0.002 ± 0.001 pct, Mn—0.003 ± 0.001 pct, N—0.0002 pct, 0-0.013 pct, P—less than 0.0002 pct, Pb—not detected, S—0.0017 pct, Si—0.0095 pct, Sn—none detected. This iron was the same as that used to make the alloys and was obtained from the same source-Vacuum Metals Corp. One specimen of pure iron from The British Iron and Steel Research Association was used for preliminary investigation. Specimens were machined to shape from cast rod, polished (the final polish being with 600 Sic paper), degreased in trichlorethylene, washed, and etched. The etching and neutralizing procedure adopted by

Jan 1, 1960

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir'e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5'11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard's method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968