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By K. Murayama, M. Kawakami, T. Takenaka, S. Yokoyama

"Cokes play an important role of spacer in blast furnace. However, they degenerate during Boudouard reaction. Blast furnace cokes are reacted with pure C02 at I 072 to 1673 K. Reaction rate was obtained by the weight change of spherical specimen. The specimen after reaction was examined by microscopic observation. The reaction rate increased with temperature and was expressed by two Arrhenius type lines. The activation energy was 126 KJ/mol at higher temperature than 13 73 K and 202 KJ/mol at lower temperature range. At the higher temperature range, the reaction proceeded from the surface leaving unreacted core, whereas homogeneously whole inside at lower temperature. The porosity increased from the center to surface at higher temperature, whereas it was almost constant at lower temperature.IntroductionThe cokes have the function of fuel, reductant and spacer to keep gas and liquid flow in the blast furnace. Thus, the reaction mechanism of coke with several gas and the strength after the reaction should be important factor to control the blast furnace operation. The reaction mechanism of coke with C02 has been studied extensively. The rate equations were derived by Gadsby[ I], Ergun[2] and Turkdogan and Vinters[3]. They were compared and discussed by Kobayashi and Omori [ 4]. Effect of crystallization degree on the reaction rate was examined by Kashiwaya and Ishii[5]. Catalytic enhancement effect of ash componets have been clarified by Kashiwaya et. al. [6]. Although degradation of coke in blast furnace has been examined recently[7], however, the degradation of coke after the reaction with C02 has not been well clarified yet. In the present work, the metallurgical coke specimen was heated in N2 and C02 and the reaction mechanism and degradation behavior after the reaction was investigated."

Jan 1, 2000

By C. Cunningham

The process of initiating opencast blasts through long cables is onerous. An obvious alternative is to replace these with radio controlled firing apparatus. Such devices appear from time to time and with the advance of telecommunications, more are likely to appear. However, there are two crucial and seemingly intractable obstacles to overcome: firstly, the problem of malfunction of the system, which can either fire prematurely or go into a state of suspense in which it is unknown whether firing might unexpectedly occur, and secondly, the problem of terrorism, as such a system could provide the capability for an off the shelf remote bomb. The issues of accessibility and electronic reliability when linked to explosives in a mining environment have to be demonstrated to be adequately covered before serious consideration should be given to these systems, up to now largely confined to military applications.

Jan 1, 2003

By J. D. Price, G. V. Woody

MANY producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. OVERCOMING DEFECTS IN COKE FROM COLORADO COALS Colorado coking coals are all of the high-volatile type and were all laid down during he Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Pocahontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-volatile coal was developed through low-temperature carbonization-or, more correctly speaking, through the partial devolatilization-of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By Jean Scott, G. A. Collins, G. W. Hodgson

WHILE it is well known that trace metals in crude •oils and distillates have been a matter of deep concern to refining engineers because of the damage done .by the metals to cracking catalysts and refractories (8, 5), the trace metals in crude oils may be of great benefit in correlation studies and in origin studies. During the geological processes in which the oil is formed from •animal and vegetable life, the hydrocarbons are subjected to a host of inter-related reactions, both physical and chemical. It has been well demonstrated that the lighter materials, certainly the short-chain paraffin hydrocarbons, are degradation products of the heavier molecules, and it might be concluded that for correlation studies it would be advisable to direct attention as much as possible not to the degradation products of the large molecules but to the large molecules themselves. Be this as it may, the methods at •hand to conduct the study are not particularly precise and, in the past, attention has centred on the simpler small molecules, as evidenced by the great mass of work involving distillation and chromatography with painstaking separation of the simpler 'front-end' hydrocarbons.

Jan 1, 1954

By Joan Melcher

The oil embargo and increasing disillusionment with nu- clear power have put this country's abundant coal reserves in growing demand. Both the government and industry are looking toward increased coal mining, and with this goes an increased interest in new and advanced methods of coal utilization. One advanced coal system stands out among the rest-magnetohydrodynamics (MHD). Its high efficiency, strong probability of sulfur dioxide control, and limited consumption of cooling water place MHD in a unique position to help the power generation industry. Another point in MHD's favor is the capital costs of operation, which are lower than those of other advanced technologies. However, initial costs are higher and realization of a commercial MHD plant in this country may be more than a decade away.

Jan 12, 1977

By Ximena Diaz

Mercury is one of the most undesirable contaminants in gold bearing ores. During cyanidation mercury cyanide compounds accompany gold in all the extraction and recovery processes. Of course mercury in the carbon eluates creates environmental problems in subsequent refining steps. One possible process alternative for the separation of gold from mercury in such concentrated alkaline cyanide solutions is the selective solvent extraction of gold by undiluted Dibutyl Butyl Phosphonate (DBBP). In order to describe the behavior of mercury during extraction by DBBP, the results from a preliminary research program are presented. In this study, temperature and cyanide concentration have been found to be the most significant variables which influence the separation of gold from mercury by solvent extraction using DBBP. It was found, using plant eluate from a carbon strip, that excellent separation of gold from mercury can be obtained at 60' C with 98% gold recovery and complete mercury rejection in a single stage of extraction. The influence of pH is also discussed in terms of the extraction chemistry. These results complement previous research which described the DBBP solvation extraction of an aurocyanide ion pair. In addition, these results extend our understanding of the alkyl phosphorous ester extraction systems by illustrating that neutral ionic species such as Hg(cN)02sq, can be extracted at low cyanide concentrations, a phenomenon which had not been observed previously for other cyanoanions.

Jan 1, 1993

By H. R. Stahl

FIVE mills are operated in Southeast Missouri by the St. Joseph Lead Co.; these have a total rated capacity of 24,300 tons per day divided as follows: Federal, 12,000 tons; Leadwood, 4800 tons; Desloge, 3600 tons; Bonne Terre, 2400 tons; and Mine La Motte, 1500 tons. These concentrators are similar in a general way, differing mainly in size and type of equipment and in minor variations in flow sheet. No attempt is made rigidly to standardize procedure in the various mills in spite of a general similarity in the ores. Each mill may be regarded as a separate laboratory in which new ideas and changes may be tried. A generalized description of the process is given, noting important differences in procedure at the various plants. The concentration process may be divided into five main stages: dry crushing, wet grinding, desliming and classification, tabling, and flotation.

Jan 1, 1947

By Thi Hien Tran, Huy Hoan Nguyen, Thi Thu Hien-Dinh, Hong Son Nguyen, Duy Anh Dao

"Lithium discovered in La Vi deposit, Quang Ngai province in the Central of Vietnam was estimated with a reserve of approximately 1.5 million tones of lithium ore, which was characterized by mainly lepidolite with muscovite, albite, and quartz. This study investigated reasonable flowsheet and optimal conditions of enrichment technology for lepidolite from the mined ore by flotation process, and producing Li2CO3 and LiCl from lepidolite concentrate by hydrometallurgical process. The significant conditions for froth flotation of lithium ore including particle size, pH of ore slurry, pulp density, chemical spending (collectors, activators, depressants, and frothers), stirring and flotation time were investigated. The identified reasonable flowsheet and optimal conditions for froth flotation the La Vi lithium ore processed lepidolite concentrate containing up to 4 wt.% Li2O with a recovery of 87.61 wt.%. The processes of sulfation roasting lepidolite concentrate using FeSO4.7H2O, then leaching in H2SO4 solution, and removing impurities were carried out to prepare a pure lithium-bearing solution for producing Li2CO3 and LiCl. The products containing 99.05 wt.% of Li2CO3 and 99.02 wt.% of LiCl were obtained with recoveries of 82.97 wt.% and 85.77 wt.%, respectively. The obtained results indicated that lithium ore in La Vi deposit can be processed to produce commercial lithium products and lead the study to develop technology for a new industry of lithium processing in Vietnam.INTRODUCTION Lithium is the lightest metal, which has many superior properties in both metal and compound (such as Li2CO3, LiCl...) states since its discovery in 1817 by Swedish chemist Johan August Arfwedson. Lithium is a favourable material for many high technology fields such as aerospace industry and chemical industry. Some industrial fields which present the main consumptions of lithium include ceramic, glass, aluminum alloy, lubricants, rechargeable Li-ion batteries, synthetic rubber, and pharmaceuticals. The worldwide production of lithium in 2014 was 31,700 tones, continually increased in 2015 of 5% presented 32,500 tones (USGS, 2016). The demand for lithium tends to increase because of the raising in consumption of lithium batteries. Lithium is mined from salar brines, mainly in Chile and Bolivia, but also from granites and pegmatites, which contain minerals with high lithium content such as spodumene - LiAlSi2O6 (Heinrich et al., 1978; Linnen et al., 2012); petalite - LiAlSi4O10 (Sitando & Crouse, 2012); zinnwaldite - KLiFe2+Al(AlSi3O10)(F,OH)2 (Paukov et al., 2010; Kondás J. & Jandová J., 2006); lepidolite - K(Li,Al)3(Si,Al)4O10(F,OH)2 (Luong et al., 2013); and amblygonite - LiAlPO4F (Garrett, 2004)."

Jan 1, 2018

By Robert E. Kirby

The potash mine and refinery of AMAX Chemical Corporation is located 26 miles east of Carlsbad on the north end of the potash producing areas. This property was developed between 1949-1952 and production of muriate began in August 1952. Two shafts, located 400 feet apart, were sunk to the ore zone 900 feet below the surface. A 15-foot diameter ore hoisting shaft equipped with a 1000-ton ore pocket, crusher and automatic skip loading equipment plus a 20-foot diameter service shaft with a curtain wall for exhausting air were provided. Sylvinite production to date has been from the first ore zone, stratigraphically, the lowest of ten identified mineralized zones in the salt section. This first ore zone has been the top producer of Muriate of Potash over the years. In our area we do have some very marginal mineralization in the third ore zone some 35 feet above the first. We have not mined from this seam as yet but we are investigating the economics very closely with access slopes and an experimental mining panel. Our ore seam is generally flat lying but does have local gentle rolling with grades from 2% to 5%. The mine was designed and developed from the beginning with conventional mining practices and rail haulage from the mining section to the ore pocket. As mining progressed in the early years, production increased from less than one million tons annually to a maximum of 3,935,000 tons in 1964. Efficiency also kept pace with the increasing production and continually improved until the efficiency of the production crews reached an average of 100.3 tons per manshift in 1964.

Jan 1, 1974

By W. G. Davenport

Chapter 13 evaluated the %02 in blast, industrial oxygen and oil requirements for smelting FeSrCuFeS2 concentrates~ This chapter examines high eu grade CU2S-CuFeS2 concentrates the same way.

Jan 1, 2001

By L. M. . Chia

The successful treatment of waste materials to recover metals with acceptable purity is often hampered by the presence of undesirable impurities. The problem is further complicated by the need to insure that any residues or solutions generated are environmentally acceptable. Hydrometallurgical processes involving leaching- solvent extraction-electrowinning offer some attractive features which address many of these problems. However, in certain instances trace impurities that contaminate the organics are difficult to chemically strip and interfere with the overall process efficiency. A new processing scheme has been developed which appears to provide some attractive alternatives for impurity removal from organics. It has been shown that many ionic impurities can be electrochemically removed from the organic by spontaneous direct reduction using solid metals. A variety of metal ion impurities have been removed from selected common organic extractants such as D2EHPA and TBP using different metals as the reducing agents. The results and probable mechanisms involved in the reactions are discussed.

Jan 1, 1994

By Sadatoshi Ohmori, Simin Zhai, Devini Abeyawardena

A road tunnel is planned to be constructed in soft, high overburden ground of around 600 m in Japan by using the center drift advancing method. The dodging effect and early ring closure of the center drift were expected to reduce the displacement and deformation of tunnel and promote safe construction. The measurement result during construction was analyzed and those effects, which the displacement and deformation after the widening excavation decreased and its effect increased as the center drift radius increased, were confirmed by numerical analysis. Also, the effect of the early closure of center drift after widening excavation did not have much effect.

Jun 23, 2024

By William J. Conrad, Ryan J. Molka, Erik C. Westman

"In order to study pillar and overburden response to retreat mining, a ground control program was conducted at a Central Appalachian mine. The program consisted of several monitoring methods including a seismic monitoring system, borehole pressure cells in the pillars, and time-lapse photogrammetry of the pillar ribs. Two parallel geophone arrays were installed, one on each side of the panel with the sensors mounted 3m (IO ft) into the roof. A total of fourteen geophones recorded more than 5,000 events during the panel retreat. A MIDAS datalogger was used to record pressure from borehole pressure cells (BPCs) located in two adjacent pillars that were not mined during retreat. A series of photographs were taken of the pillars that had the BPCs as the face approached so that deformation of the entire rib could be monitored using photogrammetry.Results showed that pillar stability and cave development were as expected. The BPCs showed an increase in loading when the face was 115 m (380 ft) inby and a clear onset of the forward abutment at 30 m (100 ft). The photogrammetry results displayed pillar deformation corresponding to the increased loading. The microseismic monitoring results showed the overburden caving inby the face, again as expected. The significance of these results lies in two points, I) we can quantify the safe manner in which this mine is conducting retreating operations, and 2) we can use volumetric technologies (photogrammetry and microseismic) to monitor entire volumes of the mine in addition to the traditional point-location geotechnical measurements (BPCs).INTRODUCTION AND BACKGROUNDExcavation of underground openings is a difficult job in a challenging environment. The rigor of the process is compounded by the lack of a method that allows quantification of changes within the rock mass as excavation progresses. Statistics kept by the Department of Labor, Mine Safety and Health Administration show that 16% of fatalities and lost time incidents in the underground mining industry are due to unexpected rock mass failure (MSHA, 2015). A recent example is the Crandall Canyon, Utah, coal mine accident caused by the vertical collapse of a longwall coal mine on August 6, 2007 (Dreger, Ford, Walter, 2008)."

Jan 1, 2016

By Douglas M. Dwosh

INLAND STEEL COAL COMPANY'S experience with a gypsum cement, with and without fiber glass filler, indicates that the concept of utilizing standard rock dust equipment to dry handle and apply gypsum cement as a mine sealant is feasible, simple and economical. Prior to 1975, Inland had casually experimented with a few sealants and had discussed the advantages and shortcomings of other sealants with various users. Hower in mid-1975, Inland foresaw the need to seriously acquire a practical sealant system. There were nearly a dozen sealant materials on the market at that time: silicate-based materials, Portland cements, vermiculite cements, gypsum cements, and magnesium-oxysulfate cements, each with their own fillers and additives. The applicating equipment ranged from simple to complex: wet mix or slurry machines operating on either a batch or continuous basis, high viscosity pumps, and pneumatic, dry conveying machines with water nozzles. Compounding the selection process, two or more products could often be used with the same machine, or a given material could be successfully applied with more than one type of machine.

Jan 1, 1976

By J. Molgaard, J. Masounave, J. Prinsen, P. Beaulieu, G. Huard

"A study carried out on behalf of the National Research Council (NRC) indicates that economic losses due to wear in the Canadian mining industry are in excess of $700 million annually. Severe wear, mainly by abrasion, was identified as the most important wear mechanism in terms of possible savings. One way to reduce losses would be the proper use of databases. A joint project of The Canadian Institute of Mining and Metallurgy (CIM) and NRC (Tribology laboratories at IMRI) has been initiated to create a factual database containing all relevant experience in the area of wear in the Canadian mining industry. As a first step, a prototype covering slurry pumps is being built. This should help to answer many questions, such as the number of people involved, interest from industry, cost vs benefits, etc.IntroductionTribology is concerned with the understanding of the mechanisms of friction, wear, and lubrication.Tribology is concerned with the correct use of materials for interacting solid surfaces, with the interaction of those surfaces with lubricants, with the chemistry, physics and use of lubricants and their additives. It is concerned with the reduction of friction and wear (or, in the case of belts, brakes, clutch plates, and similar devices, in achieving optimum friction with minimum wear) and is concerned with the avoidance of associated failures in machinery.Lubrication is usually the solution to a problem of friction and wear. Yet far from all the problems of friction and wear are solved by lubrication. The wear of grinding rods or shovel track pads can hardly be solved by lubrication, to name just two examples with which mining engineers will be familiar. There are indeed many situations of wear and friction where the surfaces in contact are unlubricated.In part, tribology is a matter of design. A major aspect, however, has to do with the choice of materials, to satisfy external constraints upon the component design or choice. The operating conditions for much industrial equipment, particularly in mining are, often very severe. The development of wear resistant materials, including materials which are applied as coatings, is clearly an important technology from the point of view of tribology."

Jan 1, 1987

By N. P. Kripakov

The Bureau of Mines has developed a unique new mine design procedure to determine the changing static load distributions imposed on under-ground support structures during the mining cycle. The procedure reduces the complexities associated with analyzing a three-dimensional problem. A combination of the multiple-seam displacement-discontinuity model and a two-dimensional finite-element window model produces refined results for a specific area of interest by assuming displacement compat-ibility between models. Input to the procedure includes the geometry of mined-out areas in up to two adjacent seams, the rock mass characteris-tics of the surrounding geology, the in situ stress conditions, and the mining sequence. The displacement-discontinuity program calculates ex-pected loadings for mine structures affected by the mining cycle and/or by overlying or underlying seams. Pseudoelastic finite-element analysis using a yield-factor approach determines the stability of coal pillars by simulating the degree and extent of nrogressive rib failure and sub-sequent load transfer. Application of the procedure is demonstrated on a field problem. In-duced stress changes predicted from the numerical model analysis are in reasonably good agreement with stress measurements obtained from an instrumented chain pillar affected by remnant workings in an upper seam.

Jan 1, 1988

By Vito J. Colangelo

The primary object of this study was to determine the effect of ferrite and its orientation upon the mechanical properties of a precipitation -hardening stainless steel with particular attention to the short-transverse properties. The investigation consisted of Jour major parts : the preliminary investigation of billet properties, the effect of forging reduction and ferrite content upon mechanical properties, the effect of notch orientation upon impact strength, and the relationship of heat composition to ferrite content. Low ductility and impact strength in the short transverse direction were found to he associated with the orientation and shape of- the ferrite plates. It was also determined that impact strength varied with notch orientation. The test values obtained with the notch perpendicular to the plane of the ferrite plate were lower than those obtained in the notch-parallel condition. The over-all investigation showed that high ferrite contents in general had a deleterious effect upon mechanical properties and that the ferrite content could he minimized by exercising rigorous control of the heat composition. A careful balance of elements, nitrogen in particular, must he maintained in order to reduce the formation of ferrite. THE precipitation-hardening stainless steels were developed to fulfill a need for high-strength corrosion-resistant alloys. In the annealed condition they are soft and ductile and possess many of the desirable characteristics of the austenitic stainless steels. In the hardened condition, the alloys exhibit the high strength and hardness of the martensitic stainless steels. The alloy under consideration in this investigation has a nominal composition as follows: C Mn Si Cr Ni Mo N 0.13 0.95 0.25 15.50 4.30 2.75 0.10 The hardening mechanism is identical to that of other hardenable steels in that it depends upon the transformation of austenite to martensite. This alloy because of its annealed structure and its ability to be hardened combines the desirable forming and corrosion properties of the austenitic grades with the high hardness and strength levels attainable with the hardenable grades. The reason for this apparent duplicity of proper- ties can be explained by considering a basic metallurgical difference between the hardenable stainless steels and those of the austenitic group. Both types are austenitic at 1800°F but, while the martensitic grades transform to martensite upon rapid cooling to room temperature, the austenitic grades remain austenitic even when cooled to temperatures below room temperature. The major difference then is in the degree of austenite stability. This stability can quantitatively be described by the Ms temperature. The Ms is defined as that temperature at which austenite begins to transform to martensite. The austenitic grades for example may be cooled to -300°F without producing significant quantities of martensite. The hardenable stainless steels on the other hand have an Ms temperature in the vicinity of 400" to 700°F. In cooling to room temperature, these alloys traverse the entire Ms-Mf range and show almost complete transformation to martensite. The semiaustenitic stainless steel, however, occupies an intermediate position with respect to its austenite stability. The analysis is so balanced that the Ills temperature lies at or slightly above room temperature. The resulting alloy retains much of its austenite at room temperature and yet responds to hardening heat treatments. Achieving this delicate balance of elements is therefore of great importance. Slight imbalances of the equivalent Cr-Ni ratios frequently result in the presence of 6 ferrite. It is the effects of this ferrit with which we are concerned, more specifically the effect of the quantity and ferrite orientation upon mechanical properties, particularly ductility. PROCEDURE A) Preliminary Investigation of Billet and Forging Properties. In order to determine the effect of ferrite on billet properties, billet stock from three heats with various ferrite contents was utilized. Tensile specimens were obtained in the transverse and longitudinal directions from this material and heat-treated as shown in Tables I and 11. Forgings were made from these same heats, the purpose being to determine what effect, if any, the ferrite might have upon the mechanical properties. These forgings were made in such a manner as to elongate the ferrite in the longitudinal and transverse directions. The method of forging was as follows. A section was cut from a 6-in.-sq billet of Heat A and flat-forged to 1-1/2 in. thick. Working was done from one direction only with no edging passes as shown

Jan 1, 1965

By M. R. Smith

Barrick Goldstrike Inc.'s Betze/Post Open Pit is located at the north end of the Carlin Trend, in Eureka County, Nevada, U.S.A. (see location Map, Figure 1). About ten open pit gold mines exist on the trend, which strikes northwesterly, through the north end of Eureka County and into Elko County. The final Betze/Post Pit configuration is shown in Figure 2, Pit Configuration. The final pit will be about 2450m long by 1550m wide, elongate in a west-northwesterly direction. The pit straddles the Barrick/Newmont property boundary. The highest elevation of the pit perimeter is 1800m at the south wall, with the east end pit bottom elevation at 1200m.

Jan 1, 1993

Some Otago quartz veins display spectacular open-space filling textures indicative of shallow formation. Fluid inclusions in some such veins show that fluid immiscibility occured before or during mineral deposition. This immiscibility or 'boiling' occured at depths ranging from about 3 km to within as little as about 100 metres of the paleo-surface. Temperatures of mineralization range from 190 - 250¦C. Metals deposited in these veins include: Au(+Ag), Hg, Sb and As. Hydrothermal alteration is confined to minor silicifation of immediate wall-rock schist, less than about two metres from the veins. These veins have some similarities to classical epithermal systems elsewhere in the world, although wall-rock alteration is much less developed in Otago. From analogy to these classical epithermal systems, it is speculated that gold mineralisation may be found beneath Otago stibnite and cinnabar localities.

Jan 1, 1987

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967