Search Documents

By J. Howard Bird

The purpose of this publication is to discuss grounding mediums and the phases of grounding related to corrosion and cathodic protection. The material presented is believed to contribute to a better understanding of this subject. It also indicates more effective methods of reducing corrosion damage to metal structures and equipment in the mining industry by cathodic protection. The authors do not intend to discuss technical aspects but rather to explain the general principles of this method of inhibiting corrosion. The relationship between soil resistivity, protective grounding, and corrosion is presented. Corrosion causes the annual loss of billions of dollars; which can be greatly reduced. Losses in the mineral industry can be excessive owing to the extensive use of direct-current power, the presence of considerable dampness, and the frequent, indiscriminate use of dissimilar metals.

Jan 1, 1958

By Will H. Coghill

This paper on milling methods and costs at a flat river (Mo.), mill is one of a series of information circulars on milling methods and costs which is being prepared by the United States Bureau of Mines, The mill under consideration treats 5,000 tons of load ore daily by table concentration and flotation. It is 25 years old, and yet it is a new mill. Research has been in continual progress at the plant since its beginning, and accordingly a day never passes without a record of change for advancement. The changes have been so orderly that no evidence of obsolete equipment remains.

Jan 1, 1932

Prof. Henry S. Jacoby, Cornell University,Ithaca, N.Y. (communication to the Secretary): When a simple beam supports any given load, the lower fibers me in tension while the upper fibers are in compression, and if its cross-section is rectangular the neutral surface, where the stresses pass through zero from tension to compression, is at mid-depth, provided the elastic limit is not exceeded. In addition to the longitudinal stresses, there are horizontal shearing-stresses between the fibers which have their maximum value in the neutral surface, and which equal zero at the upper and lower surfaces, while there are also vertical shearing-stresses. Let another beam of the same dimensions be placed on top of this one, and the load be doubled, it then produces stresses in each beam of the same character, magnitude and distribution as in the preceding case, provided there be no friction between the adjacent surfaces of the beams. Next let these two beams be so firmly united that there will be no motion between them when the same load is again applied. All the fibers in the upper beam are now in compression, and those in the lower beam in tension, while the maximum stresses in the outer fibers are only one-half as large as before. The strength of the combined beams is therefore doubled. If, however, some motion occurs between the beams, then the stresses in some of the lower fibers of the upper beam pass from compression to tension, and those in some of the upper fibers of the lower beam from tension to compression, while the stresses in the outer fibers have a magnitude between the two values previously stated. These fundamental facts relating to the flexure of beams indicate the necessity of carefully designing the keys or brace-

Jan 1, 1898

By AIME AIME

THE Engineering Education Committee of the Institute convened at the Engineering Societies Building on Feb. 18, .1929, with. E. A. Holbrook, dean of the Schools of Mines and Engineering, University of Pittsburgh, in the chair. STATISTICAL' STUDY OF STUDENTS IN MINING The first paper, a statistical study of the students enrolled in courses leading to a mining degree in 40 institutions, was presented by H. D. Keiser,, assistant editor of the Engineering and Mining Journal; who gave a brief outline of an article he was about to publish in ?that journal?. The complete article appears in the issue for March 30; 1929: To avoid repetition the results are summarized as follows: A request was sent to 42 institutions which give courses in mining' for the number of students enrolled as freshmen; sophomores; juniors, seniors and special students in mining for the years 1925-26, 1926-27, 1927-28, 1928-29. Two of these colleges replied that there were no students in mining. Students' enrolled in courses in metallurgy, geology and engineering, other than mining, were excluded from the statistics:. The statistics received were arranged in, four groups, according to the completeness of the information. One complete group of 25 institutions 'shows as follows:

Jan 1, 1929

By Sastry Putcha, Santosh Mummaneni, Swamy Avasarala, Vamshi Vemula

"This paper presents the results from a case study on the comparison of two strain acquisition instrumentation technologies, Geokon rebar strainmeters and Embedded Data Collectors (EDC) for the DC Water Main Pump Station project, in Washington D.C. These two instrumentation systems were installed by AVER in a single 18-inch (0.45 m) diameter augercast pile (with one-1.25 inch (3.175 cm) dywidag bar) at critical locations to determine the load transfer mechanism and establish a comparison between strain/load measured with these two systems along the pile. A quick static load test was performed on the test pile as per ASTM D1143 standard.Prior to the installation of the pile, a 24-inch (0.6 m) diameter outer casing was installed to the proposed cutoff elevation of -22.5 feet (-6.85 m) to discount the frictional resitance within the upper overburden zone. The pile was then drilled through the outer casing to the tip elevation of -65.02 feet (-19.8 m) with inner casing within the overburden zone. Strainmeters along with EDC were installed on dywidag bar at various locations and then wet set into the concrete following auger retrieval. The loads measured with EDC and Geokon sensors were within 15% percent of each other.PROJECT BACKGROUNDProject Background & Requirements:Like any other foundation piles, augercast piles are extensively used in the public and private sector structures in the United States for many years. It is a common practice to perform static compression (ASTM D1143), tension (ASTM D3689), and lateral load tests (ASTM D3966) depending on the project requirements. In recent years, embedded strain sensors, manufactured by Smart Structures, USA has gained prominence for its use to collect both static and dynamic measurements for driven piles. In addition, AVER has successfully used EDC for collecting long term static measurements for an abutment drilled shafts for I-95 Hotlanes project in Virginia, USA.Geokon sisterbar strain gages are widely used in the foundation industry to monitor the load transfer mechanism within pile foundations throughout the world. As the Geokon strainmeters are vibrating wire and are welded to a sister bar, there is often a debate within the engineering community with regards to what modulus to use when converting measured strains to loads. EDC sensors, unlike Geokon strain gages are embedded directly into the concrete and therefore do not have the same concern."

Jan 1, 1900

By Songsong Wang

Recently, replacing Pierce-Smith converting process with the oxygen bottom-blowing continuous converting technology has become a new research focus. Based on the principle of Gibbs free energy minimization, the thermodynamic model of oxygen bottom-blowing continuous converting multiphase equilibrium system has been established. The elements distribution behavior is calculated at the same burden composition and operation parameters as the industrial production. The results show that the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in crude copper are 0.06, 0.0030, 0.070, 0.38, 0.39, 0.020, 0.017, 0.034, 0.010, respectively, and the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in slag are 0.53, 0.81, 0.020, 0.23, 2.5, 0.0048, 0.0010, 0.0030, 1.49, respectively. The calculated results agree well with the actual industrial production data, indicating that the model can be well applied in the oxygen bottom-blowing continuous converting practice.

By L. E. Djingheuzian

"IntroductionDURING the past two decades an enormous amount of empirical data has been accumulating on grinding. These data have been obtained by mill operators on grinding ores with a diversity of characteristics, and generally they have been published. However, whenever an operator, who has started milling on a new ore, has tried to find a case in literature which would exactly fit his particular grinding problem, he has failed. Evidently, something fundamental has been lacking in all these empirical data, and, as a consequence, each new operator has had to undertake his own experimenting, get the best results he can, maybe publish these results, and let it go at that. This, in the writer's opinion, has been• due to the fact that even the ablest and most inquisitive millman has been forced to look on grinding as an art, and so, except very rarely, has not been able to find the time to stop and think; if he did so, it was rather in a philosophic way, that grinding is a fundamental process, a process that takes place in river beds, on the sea shore, etc.Nevertheless, when all the data so far published are correlated and examined as a whole, one is struck with the advances that have been made in grinding. The writer (7) had made such a study in 1949, and, when the correlation was completed, it showed that there was nothing heterogeneous about the accumulated data and that when brought together they were in harmony with each other. The writer's conclusion was that, if grinding criteria were defined and were expressed in such a way as to make integration of any data into basic formulae possible, grinding would be established as a mathematically exact science, and grinding worries of the harassed mill operator would be at an end!The first attempts to rationalize comminution were made by Rittinger and Kick. However, their theories led to endless disputes which did not accomplish much, except possibly clearing the path for subsequent investigators."

Jan 1, 1952

Large quantities of electrical and electronic equipments are discarded at the end-of-life (EOL) in different industries and house hold applications. Their disposal is creating a challenging environmental problem due to the presence of hazardous metals and non-metallic materials such as epoxy resins and plastics including brominated flame retardants etc particularly in printed circuit boards (PCBs). The recovery valuable metals and separation of hazardous materials from discarded PCBs will not only conserve the resources but also mitigate the environmental pollution. From a recycling point of view for a sustainable society, the studies have been carried out for the recovery of metal values from EOL-PCBs of DVD video players (DVD-PCBs) and vacuum cleaners (VC-PCBs) using physical beneficiation techniques. The concentration of the metals was found to be 43 wt.% and 30 wt.% in DVD-PCBs and VC-PCBs, respectively. Both the PCBs samples were ground in a hammer mill after cutting and their size analysis was carried out. The liberation of the metallic and non-metallic fractions was investigated under the microscope for different size fractions. Subsequently, froth flotation and pneumatic air separation studied were carried out to enrich the metallic constituents. The studies showed the enrichment of metals in coarser particles (-1000 +150 µm) and non-metals in the finer particles -150 µm following mechanical recycling process. A grade of 90 % with 75% recovery was achieved by froth flotation, but lower grade and recovery of 75% and 65% respectively were obtained by pneumatic separation with -1500 µm powders for DVD-PCBs. A grade of 86% metal was obtained by froth flotation with 76% recovery in the case of VC-PCBs. The lower grade of 65% with almost same recovery was achieved during pneumatic separation studies due to lower concentration of metals in VC-PCBs. The studies also showed that the froth flotation is an efficient process for enrichment of metals from both the samples. The process is environmental friendly as no chemicals are employed during entire processing. The higher recovery and grade of metal is expected to be obtained on a large scale beneficiation process.

Sep 1, 2012

By E. Morrice

This report of the Federal Bureau of Mines presents a laboratory procedure, with the requisite equipment, for electrowinning ingot (liquid) cerium metal from a fused-fluoride bath, the metal purity being about 99.9 percent. Physicochemical studies, including bath properties and electrochemistry, are included, with a speculative model of the mechanisms involved. An historical review of the methods used for electrowinning misch metals and yttrim-group metals, as well as individual rare-earth metals, is presented. The electrolytic preparation of metal from fused salt and nonaqueous media is summarized, along with the unsuccessful attempts at depositing the metals from aqueous solutions.

Jan 1, 1961

By J. E. Harris

By elimination of other possible nucleation processes, it has been demonstrated, for commercially pure magnesium and a Mg-Al alloy, that at stresses less than that necessary for triple-point cracking creep cavities are most probably nucleated heterogeneously at second-phase particles. Evidence for the existence of such particles is presented and the role of grain boundary sliding in the nucleation process is examined quantitatively. DURING creep deformation of polycrystalline magnesium and its dilute alloys in the temperature range 0.45 to 0.7 Tm (Tm = absolute melting temperature) cavities form mainly along grain boundaries oriented normal to the stress axis and failure eventually occurs by their growth and impingement.' The possibility of low-ductility creep failure of magnesium-alloy reactor cans during service has prompted a number of studies of cavity formation in these materials.2-5 In this paper divergent theories of cavity nucleation6-10 are examined critically and conclusions drawn regarding the most probable mechanism of formation of cavities in magnesium. The paper is divided into two parts. The first section consists of the review and quantitative assessment of the possible role of grain boundary sliding in the nucleation process. In the second part an experimental program is described where an electron-microscope technique has been used to determine if second-phase particles exist in as-received commercially pure magnesium and in a magnesium alloy 1) THEORETICAL REVIEW Possible nucleation sites for creep cavities are: a) high-angle grain boundary triple points,11-14 b) subboundary/grain boundary intersections,15-18 c) ledges in the grain boundary, 19-25 d) second-phase particles. 9,26-30 Each of these possibilities is now considered with special reference to deformation of magnesium. 1.1) Triple-Point Cracking. The stroh31 condition to nucleate fracture is: " > vr [1] where ss = applied shear stress, ? = surface energy, C = shear modulus, L = length of sliding interface. This relationship is independent of the nature of the interface and it is possible to calculate the stress concentration at the end of a sliding high-angle grain boundary and thus deduce, approximately,* the minimum applied stress necessary to nucleate triple-point cracking. Such theoretical predictions for Nimonic alloys have been made by McLean13 and found to agree quite closely with the minimum stress determined by experiment. Stresses capable of nucleating triple-point cracking should also be sufficient to nucleate fracture at a grain boundary due to intragranular slip, for the lengths of sliding interface in the two cases are approximately equal. Thus the minimum stress for triple-point cracking should represent a demarcation between failure due to general "cracking" and that due to cavitation. Hauser, Landon, and Dorn32 have demonstrated that for polycrystalline magnesium in the temperature range 78° to 298°K the fracture stress is inversely proportional to the square root of the mean grain diameter. As pointed out by stroh31 this result indicates that Eq. [I] describes the fracture characteristics of magnesium at low temperatures. Heal3 has reported that for rapid deformation (112 pct hr-1) of polycrystalline magnesium the transition from cracking to cavitation occurs in the temperature range 175" to 275°C. He also presented the fracture-stress values for the same material tested under similar conditions. From Eq. [I] taking G = 1.3 x 10" dynes , ? = 600 ergs . cm-2,33 and L = 0.017 cm, a Stroh-McLean13,31 tensile stress of -266 kg. cm-2 is calculated, corresponding to a transition temperature of -190°C; this is in

Jan 1, 1965

By W. G. Davenport

This chapter examines three minor influences on flash smelting's industrial oxygen and oil requirements, i.e.: (a) recycle of molten converter slag to the flash furnace (b) gangue oxides and carbonates (e,g, Ah03, CaC03) in the flash furnace feed (c) minor sulfides (e.g. NiS} in the flash furnace feed. It then examines the. sensitivity of our flash furnace calculations to previously ignored aspects of smelting chemistry -Cu, S and Fe304 in slag and 0 in matte.

Jan 1, 2001

By P. G. Bennett

The Bureau of Mines developed a process using ion exchange to recover cobalt from spent copper leach solutions. A preliminary economic evaluation of the process indicated that about one-third of the capital cost was attributed to the total resin inventory, and one-third of the operating cost was required for reagents to remove iron from the ion-exchange eluates. An agitated Pachuca elution system was investigated in place of a fixed-bed elution system. The Pachuca system reduced the resin inventory by 27 pet when compared with the fixed-bed elution system. Processing fresh spent copper leach solution reduced the resin inventory by 20 pct and resin iron loading by 80 pct. Reagent requirements for removing iron from the eluates were decreased because less iron was extracted. The Pachuca system, along with processing fresh spent copper leach solution, reduced the total resin inventory by 47 pct. A revised cost evaluation of the cobalt recovery process was obtained to determine the effects of these process modifIcations. The estimated total capital cost for a plant processing 10,000 gpm of spent copper leach solution containing 26 ppm Co was $23.1 million. With credits for nickel, zinc, and copper byproducts, the estimated net operating cost was $5.10/lb of cobalt.

Jan 1, 1988

By J. D. Davis

THE CARBONIZING properties of Chilton-bed coal from Lorado No. 5 mine, HE Logan County, W. Va., were determined by Bureau of Mines-American Gas Association tests at 600°, 700°, 800°, 900°, and 1,000° C. and by expansion tests. Chemical analyses, agglutinating and plasticity tests, and low- and high-temperature assays also were included in the investigation. Blends with low-volatile Pocahontas No. 3 coal were carbonized at. 900° C. The Chilton coal bed lies in the Kanawha, or Upper Pottsville formation of the Pennsylvanian system; the estimated original reserves are nearly 3.2 billion tons. The bed was 39/1 to 57 inches thick in the Lorado No. 5 mine, and the coal was 38 to 57 inches thick. The carbonization sample contained 62.6 percent fixed carbon on the dry, mineral-matter-free, basis, and the heating value on the moist, mineral-matter-free basis was 15,190 B. t. u. per pound; it therefore ranks as high-volatile A bituminous. It contained 1.8 percent moisture, 35.2 percent volatile matter, 57.9 percent fixed carbon, 5.1 percent ash, and 0.7 percent sulfur, as carbonized. The sulfur was largely organic, and the ash softened at 2,630° F. The agglutinating value determined on a silicon carbide-coal mixture of 15:1 was 6.8. In the Gieseler test the coal softened at 327° C., fused at 407° C., attained a maximum fluidity of 5,730 dial divisions per minute at 435° C., and solidified at 487° C. Maximum resistance in the Davis plastometer was 45.5 pound-inches.

Jan 1, 1951

By Ernest Burchard

A RECONAISSANCE of the chrome and manganese'1ore deposits of Culm was made in the spring of 191s by Albert Burch representative of the U. S. Bureau of Mines and the writer representing the U. S. Geological Survey. The object of the study was to obtain authentic information for use of the: United States Government as to the location, character, size, and availability of the Cuban deposits of the ores of these important steel-alloy metals. The Cuban Government courteously detailed Sr. E. I. Montoulieu, a mining engineer connected with the Treasury Department, to act as escort and associate throughout the work on the Island. Mr. George A. Wright, of Baracoa, Cuba, a mining engineer especially familiar with the chromite deposits of Oriente Province, was a member of the party from Feb. 25 to Mar. 20. It was possible to visit most of, the chrome-ore deposits that seemed to be of promise, but there was not sufficient time to visit all that were brought to our attention, some of which may have merit. Furthermore, no attempt was made to examine the extensive chromiferous iron-ore deposits of the Mayari, Moa, and Cubitas districts, as these deposits cannot be regarded as sources of chromium except indirectly. At the close of the field work the essential data concerning the quantity and quality of ore probably available for shipment during 1918 and 1919, in the event of the continuation of the European war, and of the tonnage of ore in reserve, were furnished to such Government bureaus as were interested, including the Shipping Board and the War Industries Board, and as soon as chemical analyses of the chrome ores could .be obtained, a press bulletin on the subject was published by the Geological Survey. In the present paper the engineering data, and tonnage estimates contained in the unpublished notes of Mr. Burch have been freely used, and their helpfulness is hereby gratefully acknowledged. Many thanks are due Senor Montoulieu and Mr. Wright for their valuable work in the field; to the officials of the Spanish American Iron Co. and of the various other companies; and to individuals holding chromite claims, for courteously facilitating the work of the party. In the study of material for the present paper, chemical analyses have been made by R. C. Wells and petrographic determinations and descriptions were furnished by Miss E. F. Bliss, both of the U. S. Geological Survey.

Jan 9, 1919

An active list of permissible explosives was published in December 1936 as part of Bureau of Mines Report of Investigations 3324, under the title "Active List of Permissible Explosives and Blasting Devices Approved Prior to July 31, 1,936." This list included 170 brand names. Changes in the list that have been authorized to June 30, 1937 placed 35 additional brands of permissible explosives on the active permissible list as a result of tests, changes in brand names, or transfer from the inactive list. Ten permissible explosives were transferred from the active to the inactive list. The present list contains 196 brand names, one explosive having been placed on the list subsequent to June 30, 1937. The brand names of the permissible explosives placed on the active list are as follows: [ ]

Jan 1, 1937

By Ivette E. Torres

World investment 10 all mineral and mining industry sectors is not available. However, partial information available provides some information useful for analysis. Information available in this section covers limited geographic information on investment in the steel industry, limited information for petroleum industry capital spending, and total U.S. foreign investment in comparison to the mineral-related sectors (tables 13, 14, and 15). Annual steel industry investment is available for the European Community, almost all countries within the European Free Trade Association (EFTA), Latin America, and other countries with significant mineral industries, such as Canada, Japan, and the United States. Although information was not available for 1992, data for 1991 indicate that for those countries aforementioned, total investment increased by 8 %. However, investment patterns were very different within the different groups of countries. While the European Community had a net increase of 12 %, dominated by an almost °40 % increase in Germany, EFTA member countries had a 26 % decrease in investment for the same period. Investment in EC countries was almost seven times that of EFT A countries. Japan's investment in the iron and steel industry, by far the largest of those available, almost twice that of the EC and almost four times that of the United States, increased by more than 20 %. In North America, investment in Canada and the United States decreased. Almost all of Latin America decreased investment in the sector. The notable exception was Mexico, with a 60 % increase. Changes in Mexico's investment policies of the recent past, its economic growth, and privatization of its iron and steel industry are some of the reasons for such an increase. The other country covered individually in Latin America, where investment in the iron and steel industry increased, although slightly, was Argentina. This limited information does not allow a comprehensive analysis of global industry trend, which in turn impacts many other mineral commodities, and with the transition in many countries within Europe and Central Eurasia that are now effecting the steel industries of the countries that were members of the U.S.S.R. and its CMEA partners, it is most regrettable that comprehensive and comparable data, both current and historic, on investment in this area are not available.

Jan 1, 1994

By Marcus A. Grossman

THE institute has established this lectureship to honor the memory of a great American metallurgist, one whose fame has continued long after his passing. As one scientist recently stated it," All metallurgical texts gradually become outdated and outmoded, except those of the great Henry Marion Howe." It seems fitting, then, that, once every year, we should review, in his honor, some aspects of the science in which he was such a distinguished leader, and also discuss any new data that may help to clarify our concepts. It is my privilege, for which indeed I express the deepest appreciation to this Institute, to offer for consideration a few thoughts on the toughness and fracture of hardened steels. Before proceeding to the data, I wish to express my great indebtedness to many associates whose stimulating discussions, generous contributions of data and cooperation in experiments are gratefully acknowledged. (But I wish to absolve them of any blame that may arise from the way in which their discussions and data have been used!) First, Dr. Edgar C. Bain, Vice President, Carnegie-Illinois Steel Corporation, whose amiable but merciless criticisms and always constructive and thoughtful suggestions help unfailingly to guard against pitfalls. Then to associates at Gary Steel Works, especially Mr. H. B. Wishart, Mr. W. K. Smith and Mr. V. Elliott, for great assistance in securing data. Also to Col. C. H. Greenall, Director of Laboratories, Frankford Arsenal, and his metallurgical staff, including Messrs. J. K. Desmond, H. Markus, D. F. Armiento, H. Rosenthal and Henry George, for numerous data and illustrations. Further to Dr. J. R. Low and Dr. M. Asimow, for helpful discussions of effects of states of stress during deformation and rupture, to Mr. J. M. Hodge for discussions and data, to the staff of the U. S. Steel Corporation Research Laboratory for advice and data, and to the Metallurgical Staff at Duquesne Steel Works. The individual acknowledgments will also be found under illustrations. Acknowledgment is also due to Mr. S. C. Snyder for incredibly meticulous scrutiny of manuscript. To all of these, grateful thanks.

Jan 1, 1946

By Pelin Altinkaya, Maria Leikola, Jussi Liipo, Mika Haapalainen, Mari Lundström, Eero Kolehmainen

With decreasing ore grades, the tailings of mining operations are becoming of increasing interest as metal-containing secondary raw materials. The objective of the current work was to investigate chloride leaching of gold, copper, cobalt, nickel, and zinc present in the flotation tailings. In the current study, the effect of cupric ion as an oxidant (0–50 g/L) and NaCl (150–250 g/L) on metals extraction was investigated. The other parameters, such as pH (1.8), temperature (95 °C), solid/liquid ratio (25%), oxygen feed rate (1200 mL/min), leaching time (24 h), and stirring rate (950 rpm), were kept constant. Gold dissolution rate was shown to increase with increase in cupric ion concentrations up to 50 g/L. Also, increase in NaCl concentration up to 250 g/L increased gold extraction. Majority of the copper present in the flotation tailings could be dissolved with all the all solutions investigated. The other base metals, cobalt, nickel, and zinc extractions were also shown to increase with increase in the cupric ion and sodium chloride concentration. However, even in the absence of cupric ion addition (t = 72 h, 250 g/L NaCl), the final extraction of Cu, Ni, Zn, Co, and Fe increased up to 98, 93, 83, 76, and 80%, respectively. This shows the power of inherently originating oxidants present in the tailings. Furthermore, the solid analysis of the leach residue indicated that leaching the flotation tailings in pure NaCl may result in partial gold dissolution. The results demonstrate that significant amount of metals present in the tailings could be extracted even with only NaCl as added chemical in the presence of oxygen feed, oxidizing agents originating directly from the raw material. This can provide an advantageous cyanide-free method for extraction of metals from very low-grade tailings with low chemical consumption.

By Y. Luo

This paper presents a number of mathematical models for predicting the different phases of the complete surface subsidence process associated with underground longwall mining. A computer program developed based on the mathematical models is briefly introduced.

Jan 1, 1992

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968