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By D. M. Deason, G. Y. Onoda

Phosphate clay wastes, as currently produced, leave montmorillonite clay in a highly dispersed and disintegrated form. Alternative processing, where the extent of swelling and self-disintegration of such clays is controlled or limited, may result in improved settling and consolidation behavior. In this study, a method to control montmorillonite dispersion, through preservation of clay tactoids, was examined. Through this process, significant improvements in settling rates and sediment solids concentrations were achieved in both pure clay systems and on simulated phosphate clay wastes.

Jan 1, 1985

By P. A. Witherspoon, Y. W. Tsang

Normal stress-fracture closure variation and stress-dependent fluid flow rates were calculated for rock fractures of different aperture distributions. This study shows that both the mechanical and hydraulic properties of the fracture are controlled by the large-scale roughness of the rock fracture. Hence the typical large-scale undulation wavelength of the rock joint dictates the suitable sample size to be used in normal stress and fluid-flow measurements, if results due purely to sample size are to be avoided.

Jan 1, 1982

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

By E. Maxwell, C. J. Bechtoldt, H. C. Vacher

IN the course of an investigation of the properties of metals at low temperature there was occasion to determine the constitution of four iridium-osmium alloys. There is very little information in the literature1 on the constitution of synthetic Ir-0s alloys. Zvyagintzev' s has made a comprehensive study of different natural Ir-0s alloys and concludes that alloys containing more than 32 pct 0s have the close-packed hexagonal structure of osmium, whereas those containing less than 32 pct 0s have the face-centered cubic structure of iridium. The alloys studied in this work were prepared by the American Platinum Works, Newark, N. J., and were received in the form of fragments approximately 1.5 mm average diameter. The fragments had been obtained by crushing ingots made by fusing charges of iridium and osmium under an arc and air cooling. The ingots were not given a homogenizing heat treatment. Sample fragments Table I. Results of X-Roy Diffraction and Microscopic Examinations Phases Present as Determined by X-ray Diffraction Osmium Alloy Close- Iridium Face- Packed Centered Osmium, Iridium, Hexagonal Cubic Mlcro- WtPot Wt Pct Structure Structure scope 0 99.9 None Present 1 23.6 76.4 None Present 1 38.7 61.3 Present Present 2 59.4 40.6 Present Present 2 79.0 21.0 Present Not detected 2 99.9 0 Present None 1 Note: Chemical analyses of the iridium, osmium, and alloys were furnished by the American Platinum Works. of the iridium and osmium used in making the alloys also were included. Several fragments of each metal and alloy were examined microscopically and by X-ray diffraction. For the X-ray method the fragments were crushed further to pass a 270-mesh screen, then sealed in evacuated fused-silica tubes, heated to 1100°C for 18 hr, and allowed to cool in the furnace. Powder X-ray diffraction patterns were obtained from the annealed fragments by means of a Norelco camera having a diameter of 114 mm, and unfiltered cobaIt radiation. For the microscopic examination several fragments in the as-received condition were mounted in Melmac, (American Cyanamid Co.) and ground using the conventional series of abrasive papers. The polishing was done with 0-2 diamond abrasive on a Microcloth (Buehler Ltd.) lap, wet with xylene. After polishing, the surface was etched electrolytically in a 10 pct solution of chromic acid or in a 10 pct solution of potassium cyanide. Both reagents attacked the osmium-rich constituent, whereas the iridium constituent was attacked slightly by the chromic acid reagent and not noticeably by the potassium cyanide reagent. The results of the X-ray diffraction and microscopic examinations are summarized in Table I. Fig. 1 shows the microstructure of a 21 pct Ir-79 pct 0s alloy. The results indicate an appreciable solid-solu-bility range of osmium in iridium as was reported by Zvyagintzev.' The solid-solubility range of iridium in osmium is more restricted, apparently less than 21 pct Ir. This implies a large range of composition in which two phases can coexist that was not reported by Zvyagintzev.

Jan 1, 1955

By Y. Takahashi, I. Iwasaki, S. Tanabe

Supported by the vigorous capital investment of the heavy and chemical industries and by the ever-increasing demand for durable consumer goods in the past decade, Japan has now emerged as the world's third largest steel producer, surpassed only by the United States and the Soviet Union. In 1968, the crude steel production is expected to exceed 50 million tons; the per capita steel consumption at that time will reach 886 lb, approaching the level of Western Europe. Characteristics of the Japanese steel industry is the high dependence of raw materials on overseas sources. Before World War II the industry relied on North China and Manchuria for coking coal, and on middle China, Hainan Island, the Philippines and the Malayan Peninsula for iron ores. After the war, the major sources of iron ores were shifted to the Philippines and the Malayan Peninsula, supplemented by shipments from the United States, Canada, India and Goa. The United States, in addition, became the primary source of coking coal.

Jan 1, 1967

By J. P. Neumann, Y. A. Chang

Lattice parameter measurements of the hcp phase in the system Ag-A1 near the stoichiometric composition Ag2Al were carried out for specimens quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K. The three heat treatments resulted in the same lattice parameters at room temperature. None of the specimens showed any superlattice lines. The lattice parameters of this alloy were also measured at temperature from 77° to 750°K. An anomaly in the temperature variation of the lattice paramete.rs occurs in the region near 400°k, which may be associated with local ordering. FROM measurements of the diffuse scattering of X-rays, it is known that the [ phase in the system Ag-A1 near the stoichiometric composition Ag2A1 ex- hibits a considerable degree of short-range order at room temperature.' Moreover, based on the position of the short-range order peaks a superlattice model had been proposed in the same study and it was suggested that lowering the annealing temperature to 420°K might result in long-range order. In the present study, the diffraction patterns and the lattice parameters of three differently heat-treated specimens, i.e., quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K, were determined from 77" to 750°K. The purpose of these measurements was to investigate 1) whether long-range order could be established by prolonged annealing and 2) whether the lattice parameters at room temperature depended on the heat treatment, since it had been proposed earlier2 that the lattice parameters in this phase are related to the atomic arrangement. 1) EXPERIMENTAL TECHNIQUES Silver and aluminum, both 99.99 pct purity, were melted in a zirconium oxide crucible under helium in

Jan 1, 1969

By AIME AIME

THE climax of the various programs and entertainments in connection with the holding of the World Engineering Congress* in Tokyo in October was the complimentary dinner given by the visiting members of the Institute to our members in Japan. At the same time President Bradley conferred an honorary membership on Baron Takuma Dan, the vice-president of the World Engineering Congress.

Jan 1, 1930

By AIME AIME

MINING geology was granted two sessions, Wednesday morning and afternoon, Feb. 17. The morning session, at which H. Foster Bain presided. first considered Paul M. Tyler's paper, "Economic Notes on Steel-making Alloys." The elements used in these important alloys are chromium, manganese, molybdenum, nickel, phosphorus, silicon, titanium, tungsten and vanadium. Edward Sarnpson and C. K. Leith asked whether chromite concentrates could be used, Mr. Tyler replying that they could if not too high in iron. G. W. Pawel said that they were used at Niagara Falls, nlixecl with coarse ore. In reply to a question asked by A. O. Hayes, Mr. Tyler said that molybdenum had not affected the price of tungsten. After this discussion, E. S. Moore's paper on nickel was considered. H. Foster Bain thought that nickel is well controlled and in good hands, technically and politically. The popular stainless steel in America is the 18:8 Cr-Ni metal. In Germany a Cr-Mn steel has possibilities. It is easy to make, cheaper. has better workability, will stand 85 per cent reduction between heats.

Jan 1, 1932

By Zárate G. E.

Practical and statistical considerations concerned with the sampling, sample preparation and chemical analysis of precious metal ores are reviewed. The principal requirements related with the characteristics of sample cutter, sample preparation, equipment and methods are discussed. The main errors introduced in the different stages of the sampling systems are defined. The application of statistical techniques to evaluate these errors to determine the ore grade variation and to design the number of increments needed to get an accurate assay are presented. Finally, results obtained with the application of this method to gold and silver ores are analyzed and some recommendations are given.

Jan 1, 1984

By Y. C. Kim, S. L. Barua

M. Armstrong's paper is very interesting and can be regarded as a pioneering work of applying geostatistics on washed coal. The density levels used in her study are uniformly spaced, which facilitated curve fitting through a proper experimental design. Most of the existing coal washing plants in the US, however, gather washability data at non-uniform intervals which, in turn, affects the goodness of curve fitting. We would like to emphasize the importance of having a proper experimental design, if a similar geostatistical application is to be conducted on washed coal. We, at the University of Arizona, tried the variogram on recovery (Kim, Barua, and Baafi, 1982, SME preprint 82-143) which showed a similar pattern as Fig. 4 of Armstrong's paper. In both cases, the first experimental variogram value is invariably and inexplicably higher than the second variogram value. Although Armstrong ignores the first point because of "small number of sample points," we did not do so because there were 17 sample pairs. As a consequence, we concluded that the obtained experimental variogram was unsatisfactory and that further research is warranted. In other words, this disagreement in variogram interpretation between M. Armstrong and the University of Arizona begs the question whether the experimental variogram of Fig. 4 truly reflects the spatial correlation in washed coal, assuming there is such a correlation. Finally, we wish that Armstrong could have done a similar study on clean sulfur, which is a vital interest to the coal mines in the US. Her implied remark on sulfur in the concluding section of the paper may turn out to be incorrect because our experimental variograms on clean sulfur at different density levels were even less satisfactory than those on recovery. ?

Jan 1, 1986

By Leon Y. Sadler, E. K. Landis

Froth flotation has been described by several authors" as being analogous to a first-order rate process. Although a few investigators"," have found orders other than one fit their data best, the rate is described most often by the first-order equation, [ ] where r is rate of disappearance of floatable mineral by flotation, C(t) is concentration of floatable mineral in the cell, t is time, and k is first-order flotation rate constant. One of the difficulties in using this rate equation to develop a mathematical description of an actual flotation process is the determination of a suitable value of the constant k. The value of k, which reflects the floatability of the floatable mineral, is dependent on the hydrodynamic conditions in the cell, type and concentration of flotation reagents used, pulp density, and pH, method of froth removal, aeration rate, particle characteristics, and many other factors. Therefore, it is reasonable to expect that each particle of floatable material has a distinct value of k and that a unique distribution of k values exists for given feed and cell conditions. This has been observed and discussed by several investigators, and mathematical descriptions of the batch cell and steady-state continuous cell with distributed flotation rate constant have been developed." The mathematical description in the form of a transfer function of the continuous or flow cell under unsteady-state conditions with a distributed flotation rate constant has not been presented in the literature. The purpose of this note is to make such a presentation. The basic features of the perfectly mixed continuous

Jan 1, 1974

By Paul F. Kerr

QUARTZ of a certain kind, is one of our strategic minerals, and Brazil is probably the one important available source. Crystals of quartz of suitable size and perfection for piezoelectrical application are rare; their most outstanding use is in radio work. Clear quartz, or "crystal," free from twinning, cracks, foreign particles of other disturbing lines of growth, and gaseous or liquid inclusions, is cut into plates which provide excellent control of frequency in broadcasting. The squares or rectangles are less than a millimeter in thickness and ordinarily on the order of 1 in. along each side. They are cut at definite angles with respect to the axes of the crystal, and ground with opposite surfaces parallel. Each small slab must be a section of one crystal, uniform throughout in atomic alignment. The thickness of the chip controls the frequency of a broadcast and it is most important to have the plates oriented and ground with utmost precision. Opposite surfaces are parallel to within 0.001 mm. and expansion or contraction due to the temperature is limited to one part in a million.

Jan 1, 1942

By Joseph W. Roe

MANY questions arising in the work of the mining engineer may be solved quickly and with sufficient accuracy by the methods of descriptive geometry; but, unfortunately, this subject is more often considered from a mathematical view-point than as an effective tool. for solving practical problems. Some of the principles involved are merged into the ordinary operations of mechanical drawing, and are used unconsciously by the engineer in his every-day work. The rest are stowed away on the book-shelf with his forgotten or rarely-used college text-books. One reason for this condition of "innocuous desuetude " may lie in the unfortunate and often cumbersome notation which it has been found necessary to introduce. If some of these principles can be recalled to the engineer's attention in terms of every-day use they may prove of practical bearing. Recently, in talking with several mining engineers, I used some of the drawing-room methods of a machine-designer, to the evident surprise of those around me. These men were perfectly familiar with the methods, but their application to mining-work had not occurred to them. At their suggestion the present paper is offered, not in any way as a treatise, but merely to suggest a certain point of view, in hope that it may lead others far more familiar with mining-problems to pursue the subject further. I. To FIND THE STRIKE. As the simplest and most fundamental problem, let it be required to find the strike of a vein when the location and elevation of three points on the outcrop are known. It will be assumed for the present that the vein is a plane.

Mar 1, 1910

By AIME AIME

ON the morning of Monday, Nov. 9, 1936, two motorcycles, with sirens screeching, - escorted a procession of 70 automobiles from the Colonia Railway Station in Mexico City to the Hotel Geneve. Riding in' the cars were just over 200 visitors- members of the A.I.M.E. and their guests. They had come, via St. Louis, in two special trains from 24 different states for the 146th General Meeting of the Institute. During the morning they and 200 others, who had come from the United States by automobile or from various cities and mining camps in Mexico, duly registered with !efficient Mme. Irma Ordoiiez de Obregon and her assistants. Then started a week of strenuous but delightful activity that will never be forgotten by the participants. They were to cover more than 500 miles by automobile, always with a motor escort, and often

Jan 1, 1937

By R. L. Mauger, P. E. Damon

Potassium-argon dating of the late Mesozoic and Cenozoic intermediate to acidic plutons and volcanic rocks of Arizona and northern Sonora demonstrates the existence of two distinct magmatic episodes. The earlier episode begins in late Campanian time and dies out before the middle Eocene. Following a quiescent period in middle and late Eocene time, magmatism increases in Oligocene time, becomes most intense at the Oligocene-Miocene boundary and dies out as the Pliocene is approached. Pliocene magmatism is primarily confined to extrusion of post-orogenic basalts. The late Mesozoic-early Cenozoic magmatic pulse is essentially confined within the limits of the classical Laramide orogeny (Laramie through Wasatch time). The mid-Tertiary pulse is contemporaneous with the mid-Tertiary Basin and Range orogeny. The Laramide provides an excellent specific example of Umbgrove's concept of the pulse of the earth and in general his concept appears to be meaningful. Copper porphyry mineralization is time-congruent with Laramide magmatism and there seems to be no doubt as to the existence of a genetic relationship between the two phenomena. Two origins are tenable: direct accumulation of the copper sulfides in the copper porphyry liquid magmatic environment; or, introduction of the mineral constituents entirely from a larger source magma when the host rock is already crystalline. Transgression and regression of the epicontinental seas provide an excellent indicator of orogeny and epeirogeny. There was an overall transgression of the epicontinental seas from early Triassic time through the Turonian epoch in early late-Cretaceous time. Thereafter, there is a relatively continuous regression of the seas until the present time. Both the earlier transgressive episode and the later retreat are intermpted by temporary but distinct reversals. These interruptions can be correlated with classical orogenies. There are six distinct orogenies so indicated in the Mesozoic-Cenozoic eras. These occur at approximately 35 to 40 m.y. intervals. The regression of the epicontinental seas following the Turonian epoch was contemporaneous with the deepening of the Pacific ocean basin over the Darwin Rise. As the Darwin Rise was collapsing the East Pacific Rise was being elevated. The Western United States, situated on the eastern flank of the East Pacific Rise, was upwarped and tilted toward the east. Epeirogeny is the primary consequence of processes that operate on a global scale. Orogeny is an exothennic process that is limited in space and is treated here as a secondary consequence of epeirogenic-initiated warping. The off-campus buildings of the University of Arizona Geochronology Laboratories rest on the volcanic rocks of Tumamoc Hill. From this hill, the observer may obtain a beautiful view of typical Basin and Range topography. The city of Tucson lies below, contained within the broad Santa Cruz basin and surrounded on all sides by characteristic NW-SE trending ranges towering as much as 7000 ft above the valley floor. Since the senior author arrived in Tucson eight years ago, a great deal more has been learned about the geochronology of this and neighboring basins and ranges. For example, the volcanic rocks underlying the laboratory at Tumamoc Hill were shown on the state geologic map as Quaternary basalt. A student of the senior author has demonstrated that the so-called basalts are in fact alkali-andesites (Halva, 1961), and we now know that these alkali-andesites or doreites (Mielke, 1965) are of early Miocene age rather than Quaternary age (Bikerman and Damon, 1965). Is it any wonder then that geologists disagree on the nature and time of Basin and Range volcanism, plutonism and tec-tonism? The plain fact is that few definitive Cenozoic fossil sites were available upon which to base a chronology and geologists were forced to guess the ages of rocks in order to achieve the semblance of a time classification. We have now made considerable progress in developing a K-Ar chronology for the volcanic and plutonic rocks of the Basin and Range (Bikerman, 1965; Damon and Bikerman, 1965; Damon et al, 1964 and 1965; Mauger et al, 1965). It is the purpose of this paper to point out the main features of this chronology and to discuss the relationship of magma-tism to orogeny-epeirogeny during post-Turonian time. We will also discuss probable relationships during

Jan 1, 1967

By M. V. Lowry

This paper outlines the economic considerations that led to the recent installation of a thickener at St. Joseph LeadCo.'s Balmat, N.Y. mill. To incorporate storage of concentrates, they decided upon a single, unusually deep tank to be used for both storage and thickening. The abnormally high rake lift required was achieved by the novel feature of having the entire drive platform raise and lower. Initial operating problems are described along with the satisfactory solutions. Total costs for concentrate handling before and after installation of the storage thickeners are compared. In Northern New York State, the St. Joseph Lead Co. conducts a 2100 tpd zinc mining and milling operation at its Balmat Plant. Conventional crushing, grinding, and flotation is used to produce a zinc concentrate. For 32 years, from 1930 through 1962, the plant operated with the concentrates going directly from flotation to the filtering, drying, and loading facilities. All of the concentrate handling equipment, therefore, had to operate 24 hrs per day. It also had to accommodate wide fluctuations in tonnage, due to variations in the grade of ore. Many problems were thereby encountered in filtering and drying, but it was never concluded that the cost could be justified for installing a conventional, large diameter thickener. Finally, in 1963, they installed an unconventional thickener that is unusual in several respects. The tank depth is 16 ft instead of the normal 8 ft. The rakes are raised and lowered by having the main drive gear located on a movable platform. Automatic controls are programmed to raise the drive platform and rakes during one shift of storage. During the next two shifts of withdrawal, the controls are programmed to lower the drive platform and rakes. After three years of operating this unique storage-thickener, the conclusion is that a correct choice was made from several alternative schemes for storing concentrates. The various considerations involved in the final selection will here be analyzed, and the design features and installation details will be de- scribed. Operating problems and modifications made to the equipment will next be considered, and finally the effects upon filtering, drying, and loading will be reported. SELECTION CONSIDERATIONS Even without a thickener, concentrate handling had become reasonably efficient at the Balmat Mill by the year 1962. A tonnage that varied between 6 and 25 tph was being handled fairly satisfactorily. The filter cake moisture of 8%% seemed quite respectable, except that two large filters were usually in service. Three filters often had to be operated in order to prevent excessive filter overflow with consequent loss of values. This situation occurred when zinc concentrates from flotation exceeded 20 tph and when filter cloth blinding developed. Over the years, numerous small improvements had been effected, such as: selection of a filter cloth with better flow characteristics; addition of flocculant to the filter feed; and, in 1953, the smallest of three drum filters was replaced by a five disc, 8' 10" diam filter with a bottom agitator and snap blow. As another example of fairly efficient operation, the oil-fired dryer was doing a seemingly satisfactory job of further reducing the moisture content to an average of 3%. However, there were often considerable dust losses when the tonnage suddenly dropped off to 6 tph. At high tonnage rates, the resulting high moistures of 4% and 5% caused difficulties due to concentrates sticking and freezing in chutes leading to the box car loaders. (Drying of concentrates is justified because of the high freight rate for the long shipping distance to the company owned smelter at Josephtown, Pa. near Pittsburgh.) It was long realized that installation of a thickener would permit the subsequent steps of concentrate handling to proceed more smoothly and would alleviate the problems existing in the filtering, drying, and loading operations. It was also realized that even a slightly lower filter cake moisture could mean considerable savings in fuel oil. However, all these factors were never quite sufficient to warrant the expense of a thickener until three more considerations were added to the picture. First, the advent of flocculants meant that a thickener of relatively small area could now be considered. Secondly, a complete renovation of the zinc flotation circuit was made between 1957 and 1961. The

Jan 1, 1967

By Milton E. Wadsworth, R. Ted Wimber

Cobalt sulfate solutions containing ammonium acetate and chloroplatinic acid were reduced by hydrogen in a pyrex-glass lined autoclave in the temperature range of 170o to 232°C and hydrogen partial pressure range of 115 to 830 psia. The reduction rate was directly proportional to the hydrogen partial pressure and surface area of the pyrex glass and was independent of the quantity of chloroplatinic acid added initially. Experiments involving the variation of the relative concentration of ammonium acetate indicated that the reducible cobalt complex was probably the diacetate complex of cobalt, Co(AC)4H20, or a new mononcetate complex Co Ac, which was in solubility equilibrium with a pink precipitate of CO(AC)-4HzO. THE reaction in which a metal is dissolved by an acid to produce gaseous hydrogen and a salt solution was discovered early in the history of chemistry. In 1859 Beketoff found experimentally that this reaction could be reversed; i.e., a salt solution could be reduced by gaseous hydrogen to produce a metal and an acid. A review of work done on this phenomenon since that time may be found elsewhere., The hydrogen reduction of a cobalt salt solution is facilitated by complexing the cobalt ion. An ammonia complex of cobalt has been reduced commercially in the recovery of cobalt metal. A new reducible complex of cobalt was discovered5 when it was found that a co-baltous sulfate solution containing ammonium acetate could be reduced by hydrogen at temperatures in the region of 200°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature below its normal boiling point, a violet color became apparent, indicating complex formation. The nature of this complex was investigated5 by the addition of NH4Ac to a CoSO4 solution maintained at 85o. During the first additions of NH, Ac, the pH of the solution remained fairly constant at about 5.85. However, as the ratio of NH,Ac to CoSO, approached two, the pH rose and then leveled off at about 6.05. The absorption spectra of a Co(Ac), solution and a CoSO,, NH Ac solution were obtained at 85°C and were compared and found to be the same. These findings suggested that the diacetate complex of cobalt, Co(Ac),.4H20, was formed at 85°C. When a cobalt sulfate-ammonium acetate solution was heated to a temperature above about 165o, a finely divided pink precipitate appeared. The X-ray diffraction pattern of this precipitate indicated that it was Co(Ac), - 4H,O. In addition, it was discovered that when chloroplatinic acid, H,PtCl;, was added initially to the cobalt sulfate-ammonium acetate solution, a faster reduction was obtained. The roles of the solution complex, pink precipitate and chloroplatinic acid in the reduction process were then investigated. APPARATUS The experimental work was carried out in a two-liter stainless-steel autoclave. Adetailed description of the autoclave and the auxiliary equipment used in maintaining constant temperature and pressure may be found elsewhere.= Because the stainless steel was corroded, and also because it acted as a hydrogena-tion catalyst, an all-glass liner was fabricated such that the solution came only into contact with flame-polished pyrex glass. EXPERIMENTAL PROCEDURE The solutions used in the experimental work were prepared by dissolving reagent grade chemicals in distilled water. Although variation of the brand of ammonium acetate appeared to have no effect on the experimental results, CoSO, 7H O from the J. T. Baker Chemical Co. of Phillipsburg, N. J.,was found to give faster reductions than that prepared by Allied Chemical and Dye Corp., N. Y. The former was used throughout the course of the experimental work and was weighed up at the outset of each experiment. The ammonium acetate was dissolved to form a 6M stock solution, which was stored under refrigeration. A 10 pct solution of chloroplatinic acid (J. T. Baker Chemical Co.) was diluted to a 1.15 x 1Q2 M stock solution, which was standardized by precipitation of K,PtCl, as outlined by Scott. The appropriate volume of the chloroplatinic acid, H,PtCl,, solution was pipetted into the clean, dry glass liner. The cobalt sulfate-ammonium acetate solution, which had previously been saturated with

Jan 1, 1962

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By C. Graeme-Barber, R. L. Bell, T. G. Langdon

An analysis is made of the formulas and ,methods used to estimate the contribution of grain boundary sliding to the overall strain of a polycrystal. The errors involved in the approximations and/or ,mistakes in earlier work are assessed quantitatively so as to make possible the critical use of previously published data. SINCE it has been found that, under conditions of very slow creep, the strain due to grain boundary sliding (?gb) may contribute as much as 80 pct of the total creep strain,1,2 it is obviously important to have reliable methods for estimating this grain boundary strain. In two recent papers Stevens3,4 has drawn attention to the pitfalls encountered in assessing ?gb. He criticizes 1) the assumptions made in the derivation of some of the formulas for ?gb, and 2) the indiscriminate averaging procedures used for obtaining the quantities substituted in these formulas. These and further criticisms of earlier work are mostly valid. Unfortunately the only formulas and procedures recommended are either impossible or very difficult to apply in practice. Furthermore no attempt is made to assess the errors involved by the earlier approximations or mistakes, and so it is not possible to make critical use of any of these early dab. The present article attempts to improve on these shortcomings by reference to empirical verification of easily applied formulas whose theoretical derivations involve some otherwise unjustifiable assumptions, and by a quantitative assessment of the errors in previous work. DEFINITIONS First it is necessary to define the terms and symbols to be used. The choice of symbols preferred here is a logical combination and extension of the v introduced by McLean5 and the u by Brunner and rant.' In Fig. 1 the two grains X and Y are displaced by the sliding vector AC. u is the component of sliding resolved along the stress axis, v is that measured perpendicular both to the stress axis and to the specimen surface, and w is that measured perpendicular to the stress axis but in the plane of the surface. Two angles define the orientation of the grain boundary: 8, between the stress axis and the surface trace of the boundary, and +, the internal angle on a longitudinal section cut perpendicular to the surface. In computing the strain resulting from the boundary displacement at all the in- dividual boundaries in a polycrystal the components u, v, or w are sometimes averaged along a longitudinal line (i.e., parallel to the stress axis), sometimes along a transverse line, and sometimes at randomly chosen boundaries. Averages obtained in these three ways are given subscripts 1, t, and r, respectively. Stevens rightly calls attention to the possibility of non-equiaxed grain shapes either at the start or at the end of deformation. In this article all values of numbers of grains per unit length will refer to measurements made before deformation. The subscripts 1 and t will be used for the number of grains per unit length obtained along longitudinal and transverse lines, r for that obtained by averaging along a number of randomly directed lines. FORMULAS FOR ?gb ?gt, as a Function of u. An obvious truth is that cgb can, in principle, be obtained by summation of all the v components at the boundaries intersected by a longitudinal line of known length I, viz.: where nl is the number of grains per unit length, parallel to the stress axis, in the unstrained specimen. There are assumptions in the analytic derivation of Eq. [I] due to Brunner and rant' but ~achinger' arrived at Eq. [la] by a rigorous method. Unfortunately the experimental procedure required by Eq. [ la] proves very difficult as boundary migration tends to obscure the points at which the longitudinal line meets the grain boundary and the errors on such measurements tend to be large, see Fig. 2. For example, on a specimen of Magnox AL 80 at a creep strain of 9.7 pct, 300 measurements of u obtained from the points of intersection of a longitudinal line with the grain boundaries gave ul = 8.95 ± 3.58 pm, or an error of ±40 pct, at the 95 pct confidence limit. These large errors due to migration may be avoided by measuring u from the separation of the segments

Jan 1, 1968

By D. F. Stein

In spite of the apparent usefulness of autoradiography in demonstrating segregation, it has had very limited success in demonstrating grain boundary segregation. Because of this limited success, a model system amenable to mathematical analysis was devised to determine which variables in the experiment are most important. As a result of these calculations, it was concluded that autoradiograPhy is a rather insensitive technique to measure grain boundary segregation. The range (energies) of the emitted particles (ß and a) must be low, and the concentration of the radioactive speczes at the grain boundary must be (in general) two or three orders of magnitude greater than the concentration within the grain. Because of these very restricted conditions , the limited success of the technzque is not surprising. In spite of the apparent usefulness of autoradiography in demonstrating segregation, it has had very limited success in demonstrating grain boundary segregation. Sulfur segregation in iron1 and possibly polonium segregation in Pb-5 pct B1 2 alloys are the only autoradi-ography experiments that have demonstrated segregation to grain boundaries in metals without the formation of a second phase. Segregation to a boundary without the formation of a second phase is often called Gibbs' absorption and is discussed by McLean in Chapter 5 of Ref. 10. There are several394 experiments showing grain boundary diffusion of a radioisotope, but this type experiment is not representative of equilibrium between the concentration of an element at a grain boundary and that in bulk, so it will not be discussed in this paper. In an attempt to determine if temper embrittle ment of low-alloy steels was associated with segregation of antimony to grain boundaries, a program to use auto-radiography (using Sb-125) was initiated. Even though other measurements strongly suggest that segregation is occurring during embrittlement, no evidence of grain boundary segregation was observed in the auto-radiography experiments. An attempt was also made to detect segregation of carbon (using C-14) to grain boundaries in iron during slow cooling. There is again strong indirect evidence7 that segregation occurs during such a treatment, but the autoradiography experiment gave no evidence of such segregation. Because of the failure of these experiments and the general lack of success by our metallographic unit in measuring grain boundary segregation using autoradi-ography, a model system amenable to mathematical analysis was devised to determine which variables in the experiment are most important. MODEL SYSTEM The model system is illustrated in Figs. 1 and 2. It is a semi-infinite bicrystal with a single grain boundary perpendicular to the top face. The width of the grain boundary, W, is defined as the region to which segregation has occurred and it is assumed that this region is of constant composition. The assumption of an infinite dimension is for mathematical reasons but the results of such an analysis (as will be demonstrated later) are valid for even very small specimens. It also is assumed that the measurement is not limited by means of detecting the radiation (photographic emulsions, counters, and so forth) but that the means of detecting radiation is linearly sensitive to the radiation and has infinite resolving power. The distance y is the perpendicular distance from the center of the grain boundary to the point at which the background radiation is measured and x is the integration variable. CALCULATION FOR BETA PARTICLES Two values of the intensity of radiation will be calculated, the intensity at the center of the grain boundary and the intensity far from the grain boundary. The radiation at the center of the grain boundary can be calculated in the following way. Assume a grain boundary of width W having a uniform concentration equal to Cgb + Cb where CGb is the excess concentration of the element under consideration at the grain boundary and Cb is the bulk concentration. The intensity of radiation, IgB, at the center of the grain boundary, is a consequence of the amount of radioactive material, decay rate, absorption, and geometrical factors which can be represented mathematically by the following expression:

Jan 1, 1968