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By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By NORMA D. MACFADDEN

WHILE the library work of the Woman's Auxiliary to the A. I. M. E. was founded three years after the formation of the Auxiliary, its present policy of establishing permanent libraries in mining camps throughout the United States dates only from 1924. Since then sixteen libraries have been established and thousands of books have found their way to homes of far-away miners, bringing pleasure and knowledge to a multitude of Americans and future citizens. Library work was initiated under the presidency of Mrs. H. W. Hardinge in 1922 and firmly established with her aid as one of the main activities of the Auxiliary. The first chairman served but a short time and Mrs. A. O. Ihlseng then took over the work of chairman of the Library Committee. To place the surplus books of Auxiliary members and their friends in use in mining camps was the immediate work of the committee. This was accomplished by placing a traveling library in the Bureau of Mines' cars and also by sending books for distribution to section chair- men in our larger mining camps.

Jan 1, 1929

By A. S. Bower

Any process which has for its object the preservation of iron and steel from rust, and which will make these metals more applicable than they now are to the requirements of mankind, will be sure to meet with attention from members of this association, and from all those who are either engaged in the extraction of the ore, its reduction to metal, or the subsequent application of the metal itself. It is, perhaps, not too much to say that when iron and steel are rendered secure against corrosion and decay, they will be used to an indefinitely greater extent than they now are. The whole realm of science has, therefore, been explored in the attempt to discover some method by which the formed article may be preserved, leaving its strength undiminished by the destructive action of rust. Paints, oils, varnishes, glazes, enamels, galvanizing, electro-depositing and what is called "inoxidizing" are among the many systems now in vogue to effect the preservation of iron and steel from the corrosive action of air and water. The object of this paper is to show what may he done in protecting iron and steel from rust by forming upon their surfaces a film of magnetic oxide by an inexpensive process. It is no new thing to be told that magnetic oxide of iron is unaffected by exposure to the atmosphere or to salt water for any length of time. The black sand of Taranaki, in New Zealand, is a sufficiently good example of this. Dr. Percy has pointed out that the reason why Russian sheet iron is less affected by exposure than ordinary sheet iron is because of a coating of magnetic oxide; but this was not known

Jan 1, 1883

By George F. Learning

TOTAL DIRECT IMPACT The uranium mining industry's principal economic impacts on the Texas economy are the result of three flows of money from the industry into the remainder of the state's economy. These three are: (1) money paid to individuals (personal income) ; (2) money paid to other businesses (business income); and (3) money paid to state and local governments (government revenues). As these direct payments from the uranium industry to various other sectors of the Texas economy subsequently circulate and recirculate within the state, the indirect effects of uranium mining's direct impacts multiply to reach amounts significantly higher than the direct income flows alone. Over the past decade, the uranium mining industry has substantially increased its role as a provider of jobs, personal income, business income, and government revenues in Texas. The growth has come almost exclusively in a largely rural, seven-county area that lies within the triangle formed by the Laredo, San Antonio, and Corpus Christi metropolitan areas. The uranium mining industry, in fact, has been the major dynamic element in this rural area despite relative stagnation in most of the region's other basic economic sectors. Over the three years from 1976 to 1978, the South Texas uranium mining industry directly contributed a total of $115 million to the economy of the seven- county region in which it operated and $164 million to the economy of the entire state of Texas. In 1979 alone, the total direct contribution of the industry to the Texas economy had climbed to $124 million in personal, business, and government income. PERSONAL INCOME IMPACT In the period from 1976 through 1978, the South Texas uranium mining industry provided an average of $12.5 million in personal income each year directly to residents of Atascosa, Bee, Duval , Karnes, Live Oak, McMullen, and Webb counties -- the seven Texas' counties that make up the South Texas Uranium Belt. A1 though 84 percent of this resulted from the employment of area residents in uranium industry jobs, some amounts were also provided by the payment of rents and royalties to land owners for the use of their land and mineral rights in uranium mining operations. In 1979, the uranium industry provided approximately $38 million to residents of the Uranium Belt and the rest of Texas. This was more than double the average of $16.1 million provided to Texas residents during the 1976 to 1978 period. The full importance of the uranium industry as a source of personal income, however, should not be reckoned merely by the amount of wages and salaries that it pays directly to its own employees, nor by its rent and royalty payments paid directly to land and mineral rights owners living in Texas. The added payments that the industry makes directly to other Texas businesses and state and local governments in Texas are themselves converted into personal income as those business firms and government units in turn pay their employees. All of the direct income payments made by the uranium industry circulate and recirculate within the state's economy, multiplying their impact as they go, until they eventually all leak out of the state as federal taxes or as payments to individuals or businesses located outside of Texas. The combined circulation and recirculation of the direct personal, business, and government income that was provided by the-uranium industry in Texas during 1976, 1977, and 1978 resulted in an average annual amount of indirect personal income of more than $83 mill ion. This alone was $20 mill ion more than the industry's average annual sales during the same years. The total of combined direct and indirect personal income contributed to the Texas economy by the uranium mining industry in that same three-year period thus averaged almost $100 million annually. In 1979, the amount of indirect personal income contributed to the Texas economy by the circulation of uranium mining's direct contributions had risen to about $196 million, more than double the average of the previous three years. The combined direct and in- direct personal income impact in 1979 thus amounted to $234 million. BUSINESS INCOME IMPACT The income provided directly to other Texas business firms through the purchase of needed goods and services by the uranium industry has been twice as big as the industry's payrolls. In 1976, 1977, and 1978, the South Texas uranium industry spent an average of almost $36 million each year to buy both goods and services from other Texas businesses. By 1979, this direct contribution to the Texas economy had swollen to $76 million. The biggest share of the uranium industry's payments to other businesses have gone to contracting firms, including both construction firms and those providing specialized mining services. In the past four years, about 40 percent of the direct payments made by Texas uranium producers to other Texas firms have been to contractors. Texas wholesale and retail firms have also shared in the business sales provided by the South Texas uranium mining industry. Over the past four years, Texas wholesale and retail trade businesses have accounted for about 34 percent of the uranium mining industry's purchases from other Texas businesses. Public utilities firms have received another six per- cent, while Texas manufacturers and transportation firms have accounted for about five percent each. The other sectors of the state's economy, including other mineral industries, agriculture, finance, insurance, real estate, and services, have accounted

Jan 1, 1980

By Paul T. Allsman, E. W. Newman

TRENCHING, sampling, and core drilling in Stillwater and Sweetgrass Counties, Mont., by the Bureau of Mines have delimited over 5,000,000 tons of chromite ore containing more than 20 per cent chromic oxide. The Benbow and Mouat-Sampson mines have been developed and are fully equipped for mining and milling 500 tons and 2000 tons a day, respectively.

Jan 1, 1944

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By V. N. Mackiw

IN the process employed by Sherritt Gordon Mines Ltd. for the production of metallic nickel, a sul-fide concentrate is leached with ammonia and air under pressure. Following the removal of iron, copper, and other impurities, there remains a purified solution having the following analysis: 40 to 50 g per liter Ni, 200 to 400 g per liter (NH4)2 SO 4, and 20 to 30 g per liter NH3. Metallic nickel is reduced from this solution by hydrogen under pressure at 300' to 350°F in mechanically agitated autoclaves. A catalyst, ferrous sulfate, is required to initiate the first reduction. After the reduction, the depleted solution is discharged, leaving the metallic nickel in the autoclave. The nickel produced, being in a finely divided form, is used as a catalyst for the reduction of the next batch of solution. Upon repeated use the metallic nickel particles increase in size and become more compact, resulting in the production of a powder with higher apparent density. For this reason, each reduction is termed densification. Finally, when the burden of metal powder in the autoclave becomes too great to obtain effective agitation, both powder and depleted solution are discharged. The autoclave is then filled with fresh solution, ferrous sulfate catalyst added as before, and a new cycle started. The operation is described in earlier publications.1-6 A comprehensive historical review of the reduction of metals from solutions in general was given in a paper by Schaufelberger.7 The experimental data presented in this paper were taken from the work done in the Research Laboratory of Sherritt Gordon Mines Ltd. in Ottawa during the development of the process in 1951 and 1952. The results of the work were tested on a pilot plant scale in Ottawa in the period 1952 to 1953. Following laboratory and the pilot plant studies a commercial process has operated successfully since 1954 in the Nickel Refinery of Sherritt Gordon Mines Ltd. in Fort Saskatchewan, Alberta. General Experimental Technique The experiments were carried out in a stainless steel, 1-gallon, agitated autoclave designed and manufactured by Autoclave Engineers Inc. The inside dimensions of the vessel were 5 in. diam and 12 in. depth. The stirrer consisted of a 1/2 in. diam shaft 11 in. long fitted, with an axial flow type impeller (three blades bent to throw downwards) and a radial flow

Jan 1, 1958

By Walter Kauzman

ALL viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.[t] Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem -i.e., the dependence of shear rates on temperature, stress, etc.-from the standpoint of recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of applications.1 RESOLUTION OF MACROSCOPIC SHEAR INTO MICROSCOPIC MOVEMENTS; RESEMBLANCE TO CHEMICAL REACTIONS Just as any large body is made up of many small units, or atoms, so macroscopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for nonturbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove. In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker,4 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the

Jan 1, 1941

By H. R. Peiffer

Hardening of soft metals can be accomplished by dispersing finely divided hard particles in them. The dispersing of finely divided alumina in silver in the presence of oxygen yields a high strength material which is unusual in that its mechanical properties above the melting point of the continuous Ag-O alloy matrix are similar to other solids. The tensile strength is studied for two of these alloys, one of which contains 15 pct by weight alumina and the other 20 pct by weight alumina. The average fracture strengths above 960°C of these alloys were found to be 0.4 x106 dynes per sq cm and 3.8x106 dynes per sq cm respectively. The strengths appenred to be independent of temperature above 960° C. The creep behavior of the 20 pct alumina material was studied above 960°C. The initial creep rate, 6 , of this material can be represented by where s is the applied stress and E the activation energy for the process. This energy is of the order of 1.7 to 2.1 ev. HARDENING of soft metals by the addition of finely divided, hard particles has resulted in the production of materials with excellent creep resistance and with inhibited recrystallization.' It has been demonstrated that such composites have useful strength up to temperatures very near the melting point of the soft metals, but one might expect that the strengthening by the dispersed particles ceases to be of importance above the melting point of the softer phase. This, however, is not so.2 In this paper the strengthening of a liquid Ag-O solution by the presence of dispersed alumina is discussed and experimental data concerning the mechanical properties of such a material at temperatures above 960°C presented. EXPERIMENTAL PROCEDURE Specimens were prepared using powder metallurgical techniques. Finely divided silver oxide was mixed in the appropriate proportions with "Linde B" alumina. For these experiments the specimens contained 15 or 20 wt pct alumina in pure silver.* These alloys were used in these experiments since they were the ones that could be handled readily enough to yield experimental data. Silver oxide was used in preference to silver because it is readily available in a very finely divided form and because the presence of excess oxygen in the silver is important to the properties2 of the material. The powders were mixed wet, using alcohol as the medium, in an ordinary food blender until a uniform mixture was obtained. They were then dried and heated to reduce the silver oxide to silver. Only a fraction of the finely divided silver remains unoxi-dized upon removal from the oven since the finest particles of silver oxidize immediately upon contact with air. The remaining fine silver served as a binder during pressing. The mixture was then pressed at 20 tons per sq in. into shoulder-grip (reduced section 1/4 in. by l/4 in. by 1 1/4 in.) and rectangular bar specimens (l/4 in. by 1/4 in. by 2 in.). The green specimens were heated very rapidly in a globar furnace to 1000°C, held at temperature untic they had reached theoretical density and then furnace cooled. The strength of the two compositions at temperatures above 960 °C was determined by pulling shoulder grip specimens inside a furnace mounted on a tensile machine. Specimens were gripped by means of wires wrapped around the shoulders of the specimen. Temperatures were measured by means of a chro-mel-alumel thermo-couple placed in the vicinity of the specimen. Control of temperature (within ±°15C) was accomplished by means of a Weston Recorder-Controller. Before loading, specimens were held at temperature for approximately 15 min in order to insure uniform specimen temperature. The low loads were measured by a special load cell designed by Baldwin Lima Hamilton. All testing was performed on a FGT testing machine of the same com-pany. Creep studies were performed in bending utilizing rectangular specimens of the 20 pct alumina alloy. Specimens supported at both ends by knife edges of inconel were placed in a globar furnace, heated quickly to temperature, and the deflection of the beam measured optically as a function of time. The weight and size of the specimen were predetermined and the maximum stress on the beam calculated from

Jan 1, 1962

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By Garth M. Crosby

Hugh E. McKinstry (Professor of Geology, Laboratory of Mining Geology, Harvard University, Cambridge, Mass.) Pre-Cambrian age for the Coeur d'Alene mineralization, as indicated by isotope studies and recently discussed by Silverman, Long, and Kulp' would explain some features of the mineralogy of the district that have long been a puzzle. In the Silver Belt, especially in the Sunshine mine, lead-zinc min erali zation passes downward into tetrahedrite ore. Although commercially speaking this is a rich silver zone, the silver is, quantitatively, a mere impurity amounting to a small fraction of 1 pct. In effect the zonal change is from lead-zinc down into copper mineralization—-the usual zonal change that occurs in many districts. In the Burke-Mullan portion of the district, on the other hand, lead-zinc ore does not pass downward into copper mineralization of the Sunshine type. Instead, pyrrhotite appears in depth while the tenor in lead and zinc declines. The change occurs at increasingly greater depth away from the Gem stocks, deepening irregularly by some 3000 ft within two to four miles. As noted by Crosby, biotite, grunerite, and garnet appear in the deep zone. The marked difference between this apparent zonal change and the more nomal change to a copper zone is quite explainable if already existing pre-Cambrian veins have been locally metamorphosed by a Tertiary intrusive. The chief obstacle to this explanation is the evidence that mineralization cuts Laramide intrusives, but evidence on this point is conflicting as indicated by Crosby's observations and summary. This is not the first instance of a problem in determining the time-relationship of mineralization to a spatially associated intrusive. At the Noranda mine veins of chalcopyrite extend into a diabase dike which apparently cuts the ore, although Price2 concludes that the ore is later. However, at the Normetal mine diabase of a similar dike is thought3 to intrude the orebody but is cut by stringers of chalcopyrite. In the Sullivan Mine, B. C.,4 galena follows a fracture in a larnprophyre dike which, itself, cuts the main orebody. In the Sudbury district dikes of olivine diabase are clearly younger than the nickel ore, yet where they cut the Creighton orebody they contain stringers of chalcopyrite. In the laboratory, Hawley5 has developed veinlets of sulfide (chalcopyrite) it] silicate gangue by heating specimens of ore in a stream of H2S at 410 °C. From this and other evidernce. it seems clear that sulfides can be transferred from one site to another — at least through short distances — at temperatures well below their melting points. It would seem then that even if sulfide Mineralization in the Gem stocks can be shown unequ ivocably to be later than the intrusive the possibility of "remobiliza tion" need not be more than local. Thus the zonal relationships are quite in accord with a pre-Cambrian age for original deposition of the lead, zinc, copper, silver, and uranium in the Coeur d'Alene district. REFERENCES 1. A. Silverman, A. Long, and J. L. Kulp: Discussion of: The Gem Stocks and Adjacent Orebodies, Coeur d'Alene District, Idaho. Mining Engineering, May 1960, pp. 470-471; AME Trans., 1960, vol. 217, p. 117. 2. Peter Price: Geol. & O. D. at the Home Mine, Noranda, Quebec. Can. Inst. M & M Bull 263, 1934, p. 108; also,Trans. CIMM 1939, pp. 108-140. 3. w. L. Brown Nometal Mine in structural Geology of Canadian Ore Deposits, Montreal, 1948, p. 690. 4. C. O. Swanson and H. C. Gunning: Geology of the Sullivan Mine. Can. Inst. Mining & Met. Trans. vol. 48, 1945, p. 653. 5. J. E. Hawley: Heat Effects on Sulphides and Possible Applications. Univ. Toronto Studies, Geol. Ser. No. 46, 1941, p. 34.

Jan 1, 1961

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By R. A. Graham, R. W. Rohde, J. R. Holland

In a shock wave compression study of a martensitic Fe-30 pct Ni alloy, Graham, Anderson, and Holland' found a region of unusual compressibility extending from a few kilobars up to about 20 kbars. This region was characterized by a continuously decreasing shock wave velocity with increasing stress. In this note, we report the results of a study initiated to determine the source of this unusual compressibility. In earlier shock-loading experiments on martensitic Fe-30 pct Ni, Loree et a1.' determined that a phase change occurred at about 80 kbars. Subsequently, Bowden and elly found that samples of a similar material shock-loaded at about 100 kbars experienced a martensite-to-austenite transition. Their crystal-lographic analysis showed the transition was a direct reversal of the established martensite system to the austenite phase. The shock loading in the present experiments was accomplished by precisely controlled plane impact between two discs of the sample material. This configuration created a state of uniaxial strain in the two the front of a projectile which was accelerated to various velocities. Planarity between the impacting discs was controlled to 5 x 10-4 rad, and impact velocities were measured to 0.5 pct. From a knowledge of the Hugoniot relationships of the material and the impact velocity, the shock-wave stress can be calculated. Samples were shocked at 18, 50, 70, and 100 kbars. The specimen discs shocked at 18 and 50 kbars were instrumented with quartz gages to observe the stress time profile. A more detailed description of the experiment has been given previously.4 The shock-loaded specimens were recovered intact by decelerating them in a catcher filled with soft wood. Discs of Fe-30 pct Ni nominally 12.7 mm thick and 64 mm in diam were cut from bar stock. Chemical analysis of the material provided the following composition in weight percents: 29.5 Ni, 0.50 Mn, 0.21 Si, and 0.10 C, with traces of Cr, Cu, Mo, Al, and Co. The discs were austenitized at 650° C for 2 hr at a pressure of less than l0-' torr, and furnace-cooled. Martensite was then produced by quenching the discs at -196" and holding 168 hr. The initial martensitic structure formed is shown in Fig. l(a). Typical microstructures of samples shock-loaded at 18 and 100 kbars are shown in Figs. l(b) and l(c). The banded structure with the austenite regions running parallel to the shock propagation direction was characteristic of samples shock-loaded at all stresses. No such banding was found in samples that were not shock-loaded. Comparison of Figs. l(b) and l(c) shows that, although under the optical microscope the two microstructures are quite similar, the martensite plates of the specimen shocked at 100 kbars etched in a distinctly different manner. This unique etching behavior of martensite in samples shock-loaded above the 80 kbar transition point has also been observed by Leslie el al.' These investigators determined from X-ray and electron microscope studies that fcc martensite, similar in appearance to normal bcc martensite, had been formed under shock loading. A quantitative determination of the amount of austenite present after shock loading was made by X-ray techniques. Both the methods of Lindren' and Miller' were utilized. The results are shown in Table I. The error limits are those experimentally observed from two independent analyses of each sample and represent the precision of the experiment. The absolute error, which should be similar for each sample, is believed to be about 10 pct. It is seen that as the shock stress increases the amount of austenite present also increases. On the basis of the X-ray and microscopic observations, we conclude that shock loading below the 80 kbar ersal will initiate a martensitic reversal: the amount of reversal that occurs increases with in-

Jan 1, 1969

By P. F. Gnirk, J. B. Cheatham

An experimental investigation has been made to study the effects of tooth angle and confining pressure on the force required for indentation of dry rock samples under confining pressure. In these experiments static single-tooth indentations were made on two standstones, a limestone, a schist and a slate under confining pressures of 5,000 to 15,000 psi. Sharp wedge-shaped teeth with included angles ranging from 30°to 105°were used. In all cases the force-displarenzent curves are approxinlately linear for rocks tested under confining pressure, as contrmted with the discontinuous curves obtained for silnilar rocks at atmospheric conditions. Photonzicrographs of thin sections through the craters indicate very little evidence of chip formation during indentation. In general the experimental data lie between calculated values for perfectly rough and perfectly smooth tooth-rock interfaces. INTRODUCTION The variables associated with ctrilling at depth are numerous and, in many instances, are not easity isolated and controlled. Also, many of these variables are interdependent; however, if the variables which are sufficiently independent of each other are held constant and are appropriately introduced, the dependent variables can be more easily studied and evaluated. It is the purpose of the present investigation to study experimentally the simplest case of bit tooth-rock interaction. In essence, the experiments have involved the static loading of sharp wedge-shaped tools on the surfaces of effectively semi-infinite dry rock samples subjected to confining pressures. During this investigation the following quantities have been maintained constant: 1. Pore pressure: atmospheric (i.e., the rock is dry). 2. permeability: although the rocks may be permeable, they are "jacketed" in such a manner that the fluid is not permitted to flow through them. 3. Temperature: 75F. 4. Rate of loading: essentially static (approximately 0.002 in./second). 5. Bit tooth: a sharp wedge-shaped tooth loaded normal to the rock surface. 6. Rock surface: smooth and flat. 7. Drilling fluid: hydraulic oil. In addition to the above conditions, the rock surface was free of a layer of cuttings. There was no indexing to previously indented surfaces, and the influence of corners of the borehole was neglected because the rock samples were effectively semi-infinite. The following quantities have been varied, and the resulting effects have been studied: 1. Rock a) Type (e.g., limestone, sandstone, etc.). b) Mechanical properties ) Necessarily dependent c) Porosity on type of rock. 2. Bit tooth (included angle of wedge-shaped tooth). 3. Depth of penetration. 4. cobfining pressure. On the basis of laboratory experiments which have shown that many rocks exhibit ductile behavior at confining pressures corresponding to depths usually reached during drilling,'.' a theory has previously been advanced which predicts the force required for penetration by a single sharp wedge tooth into a ductile* material.' The material is assumed to be isotropic, homogeneous and rigidly plastic (no elastic deformation) and to obey the Coubomb yield criterion (Figs. 1 and 2). Equations governing the force required for penelration are given for two extreme cases:** 1. A smooth, perfectly lubricated tooth-rock interface (fridionless boundary), in which the solution gives a minimum value for the penetrating force: in which F = force of the tooth, b = length of tooth edge,

By D. F. Kaufman, H. R. Spedden, A. M. Gaudin

MANY studies of comminution have been made to ascertain the size distribution of the product and to evaluate the work of comminution in the light of the size distributions of the feed and product. Up to now, these studies have been essentially statistical in character, that is, a certain lot of feed was subjected to comminution in some specified way, and the aggregate product was fractionated into sizes, thereby losing all knowledge of individual relationship of feed to product pieces. Radioactive tracers offer a means to do something in this respect which could not be done before, namely, to follow the rupturing of some particular piece in its normal environment of other pieces. That is, it permits going beyond the usual statistical limitations of size distribution studies to what may be termed a personalized or individualized study. The purpose of this paper is to present some preliminary experiments conducted with this tool. The method employed was to mark radioactively some constituent of a feed. It is possible, of course, to consider the preparation of two lots of material of which one is radioactive and the other is not, and to blend the two ahead of the comminuting step; but to do so is open to the objection that the two preparations may not be identical. Therefore a technique has been chosen that removes this objection by merely taking out a size fraction of a comminution feed, rendering that fraction radioactive by exposure to a neutron flux, and then by returning it to Table I. Size Distribution of Offspring Albite Particles Originally 28/35 Mesh and in Admixture with Other Sizes After Grinding 2 min in a Steel Ball Mill Specific Activity ' Cumu- Corrected Distrl- latlve Size for Back- butlon In Distri- Fractlon ground, Weight, Product, button, of Product, cpm/gm g Pctb Pct Mesh (A). (W) (P) (ZP) + 28 0 56.0 0 100.1 28/35 62.6 54.0 24.8 75.3 35/48 62.8 59.4 27.7 47.6 48/65 41.1 53.0 16.2 31.4 65/100 29.6 45.7 10.2 21.2 100/150 23.7 37.0 6.6 14.6 150/200 23.3 25.1 4.4 10.2 200/270 20.1 19.0 2.9 7.3 270/400 17.8 21.2 2.9 4.4 -400 22.9 25.2 4.4 — 100.1 a These activity determinations were made in rapid succession in the order given. The specific activity (Ao) of the active 28/35 mesh fraction of the feed was measured at the beginning, after the measurement on the 65/100 mesh size fraction of the product, and; The end. The decay-corrected activities at those times were 246.7, 241.0. and 236.9 cpm per gm. The weight (W0) of the active 28/35 mesh fraction in the feed was 55.0. b Example of calculation for P in the 65/100 mesh oroduct frac- A W tion; A = 29.6, W = 45.7, Ao = 242.7, Wo = 55.0: P = — x — Ao Wo = 0.102 = 10.2 pet. the remainder of the charge for the comminution experiment. A relatively simple procedure was developed by which albite, containing sodium, was activated in the M.I.T. cyclotron. The cyclotron makes highspeed deuterons which impinge on a beryllium target, thereby producing a concentrated neutron flux. The mineral was exposed to this flux for 2 hr. This treatment changed enough of the sodium to sodium 24 (14.8 hr half-life, 1.4 mev ß) as to make detection and measurement easy. The nuclear reactions taking place were: 11Na23 (n,?) 11Na24 (irradiation) 11Na24 ß,?,? 12Mg24 (decay) The detailed technique of the experimentation was as follows: 40 kg of hand-sorted, lump albite were crushed to pass 10 mesh. After careful mixing of the lot, a screen analysis was made. The whole lot of material was fractionated on standard Tyler screens from 14 down to 200 mesh. Samples for experiments were compounded from these fractions in accordance with the screen analysis. When it was desired to make an experiment in which, for example, the 28/35 mesh size fraction was to be studied, the blend of size fractions was made as indicated above, except that the 28/35 mesh size fraction was added only after irradiation in the cyclotron. The blended charge containing the activated albite was ground for 2 min in a laboratory ball mill with a steel ball charge of controlled size distribution. The ground product was carefully sized on a set of Tyler screens in a Ro-tap. Each size was analyzed for radioactivity by the use of an end-window Geiger-Mueller counter and standard scaling circuit. This analysis was carried out in detail as follows: a 20-g sample was placed in a Petri dish, packed carefully to obtain reproducible geometric distribution with reference to the Geiger-Mueller tube, and the activity was counted for a 2-min period. Several determinations of the activity of the active size fraction in the feed were made at various times to establish the decay in activity with time. Linear interpolation was used to evaluate the activity that the active size fraction in the feed would have had at any given instant. The ratio of the observed activity in a size fraction of the product to the activity that the active size fraction in the feed would have had at the same time gives the fraction in the product size that came from the irradiated size in the feed. The general formula for finding the distribution, P, of a specific individual size fraction in the feed

Jan 1, 1952

By T. R. Scott

The acid pressure leaching of zinc-lead flotation concentrates from the McArthur River deposit, Northern Territory, Australia, has been studied in a three-stage, continuous, co-current system, using titanium reactors of 6 gal capacity. The starting pulp contained 2.7 lb solids per gal of synthetic spent electrolyte and the final liquors contained 120-125 gpl Zn. Parameters investigated included temperature (95-120°C), oxygen pressure (30-100 psi), acid addition (80-130% of theoretical), and leaching time (35-65 min per stage). Technical factors studied included mixing and pumping of feed, agitation, settling and washing and control mechanisms. The chemistry of liquor impurities, of scale formation in autoclaves and of lead jarosites in residues was studied in some detail. Results indicated that 90-93% zinc recovery could be obtained with a "low- acid" process, using 113°C and 70 psig with oxygen as the favored operating conditions. Residues contained 16-18% elemental sulphur and 15% lead, together with unreacted pyrite and gangue minerals. Pelletizing of residues was impracticable, and alternative suggestions for the recovery of lead, sulphur and silver are discussed. Preliminary estimates for plant and operating costs are given and enable some comparison to be made with conventional procedures.

Jan 1, 1973

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963