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By G. Ansel, J. P. Doan

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947

By Harry A. Roe

The power drag scrapers and the slackline cableway excavator have been called "long-range excavators." Broadly, their field of usefulness is restricted to work in which their long range of action permits them to operate economically, and which other, possibly more conventional, excavating units cannot do. Both of these machines dig or lift material and transport it to a remote dumping point. They combine these two functions in a single machine, nearly always in a single straight-line motion. The purpose of this paper is to examine the important features that distinguish the machines in this group from each other, as well as from other groups. The Machines The "power drag scraper" is a long-range excavating machine that employs a bottomless drag scraper operated back and forth between digging and dumping points by two haulage cables. The typical arrangement is that of Fig. 1. This is the "slusher" of the underground mine, as well as the "dragline scraper" of the sand and gravel industry, and other open-pit mining operations.

Jan 1, 1938

By Harry A. Roe

The power drag scrapers and the slackline cableway excavator have been called "long-range excavators." Broadly, their field of usefulness is restricted to work in which their long range of action permits them to operate economically, and which other, possibly more conventional, excavating units cannot do. Both of these machines dig or lift material and transport it to a remote dumping point. They combine these two functions in a single machine, nearly always in a single straight-line motion. The purpose of this paper is to examine the important features that distinguish the machines in this group from each other, as well as from other groups. The Machines The "power drag scraper" is a long-range excavating machine that employs a bottomless drag scraper operated back and forth between digging and dumping points by two haulage cables. The typical arrangement is that of Fig. 1. This is the "slusher" of the underground mine, as well as the "dragline scraper" of the sand and gravel industry, and other open-pit mining operations.

Jan 1, 1938

By Friedrich Wellmer

INTRODUCTION The Ramsbeck Pb/Zn Mine is located in the northern Sauerland area of West Germany, 150 km N of Frankfurt and 120 km E of Cologne. This is a vein deposit which has been worked from the middle of the 19th century to 1974. About 15 million tons of ore were mined and milled. The ore district contains several vein deposits and is roughly 14 km in length and 4 to 5 km in width. The host rocks are strata of Lower Middle Devonian age. The strata strike 60° to 70° NE and where overturned have a dip steeper than the veins (Fig. 1). The galena-sphalerite mineralization is in quartz veins, which are mineralized where they cut the "Main Ramsbeck Quartzite" horizon, a very competent host rock. Vein structures strike at 65º to 75º, dip about 20° to 25º SE and cut the quartzite at approximately 60 m intervals. The main or "steep veins" within each vein structure dip at 10º to 80° SE with an average of 30° and are offset by thrust faults dipping 5º N to 40° S with an average of 5º S. "Flat veins" usually weakly mineralized occur in the thrust faults between the "steep veins", thus forming the overall step-like vein structure. The mineralization is very irregular and changes a- long strike and down dip. It consists of thin veins of pure sphalerite and galena with quartz and pyrite. The thicknesses of the pure sphalerite and galena veins

Jan 1, 1977

By Leonard A. Wood, A. G. Winslow

Subsidence has occurred in several areas of the upper Gulf Coast region of Texas, although in most cases this is not evident without precise instrumental leveling. As referred to in this report, the region com- prises about 7200 sq miles of the Gulf Coastal Plain and includes all or parts of the following counties: Harris, Fort Bend, Waller, Brazoria, Galveston, Liberty, Chambers, Orange, and Jefferson (Fig. 1 ). Topographic relief is low, ranging from sea level at the Gulf of Mexico to 300 ft or more in northwestern Harris County.

Jan 10, 1959

By E. Clarence Peterson, Rip V. Thompson

ALTHOUGH the metallurgical treatment for the Ophir Hill tailings was developed more than 20 years ago and in the interim a vast amount of experimental work was done with later-developed flotation reagents, it was found necessary to revert to the original oil reagents and their combinations with specific chemical reagents in order to obtain results of economic value. This is of especial interest because in present ore-treatment investigations later-developed flotation reagents are used almost exclusively and the coal-tar derivatives, except in certain patented reagents, are virtually neglected. These coal-tar oils and derivatives still have a definite field of application, especially in the treatment of some oxidized ores when modified sulphidization is desirable. The Ophir Hill tailings deposit is in Ophir Canyon, Tooele County, Utah, about 55 miles southwest of Salt Lake City and 25 miles south of the Tooele smelter of the International Smelting and Refining Co. A road good for trucks leads directly from the Ophir mill to the smelter. TAILINGS These tailings were produced in the old Ophir Hill gravity concentrator previous to 1921. The original mill ore was a heavy lead-zinc-copper-silver-iron sulphide ore formed by limestone replacement. The gangue is a highly siliceous lime. An assay of the original milling ore would approximate 1.0 per cent Cu, 6 to 8 per cent Pb, 6 to 8 per cent Zn, 8 to 12 oz. Ag, 18 to 25 per cent Fe, 2.0 per cent CaO, 20 to 5o per cent insoluble. The gold content was 0.005 oz. or less. Tailing was impounded in a fairly wide area in a canyon about ½ mile below the mill. A number of dirt embankments were thrown up to form settling ponds and the tailing was allowed to flow through them in series. Coarser sand deposited at the upper end of the ponds and the finer slimes settled gradually as they passed through the successive settling ponds. As soon as the coarser tailings filled a pond, the tailings were by-passed to the next pond and teams and scrapers were used to haul the deposited sand onto the banks to make them higher. The final dump was approximately 2500 ft. long and 250 ft. wide at the bottoms, with banks sloping up at 45°. The coarser sands predominated at the upper ends and sides of the ponds while the proportion of slimes increased steadily at the lower ends. The lower end of the pond contained over 50,000 tons of slime tailings, 90 per cent of which passed through a 200mesh screen. SAMPLING The entire tailings deposit was sampled by drilling vertical holes so placed as to give data concerning size segregation and the contour of the underlying ground as well as to secure an assay sample. Different types of auger and post-hole drills were tried. None was found satisfactory because the stratified layers of

Jan 1, 1940

By Donald L. Ball

The equilibrium of boron nitride, gaseous nitrogen, and solute boron was investigated in Fe, Fe-C, and Fe-Si rnelts by the Sieverts technique. The free ellergy of dissociation of boron nitride, involving -the implied standard states, was evaluated in the range 1400" to 1600°C as: ?Fo = 38,000 - 23.5T, cal ber mole The solute-solute interaction coefficients eBB, ecB , and eg were determined as 0.058, 0.22, and 0.078, respectively. BORON is an important ingredient in some types of steel and cast iron. It was employed at a particularly high level, 0.01 wt pet, in the as-cast malleable iron "CentraSteel".1 In this material, the boron concentration was critical in order to assure graphite, and avoid primary cementite, in the as-cast structure. One possible function of the boron in this alloy was the nucleation of graphite through the agency of boron nitride, which, conceivably, precipitated from the melt during cooling. A research program was instituted to assess the validity of this proposed mechanism. The first undertaking, reported here, was a determination of the thermodynamic possibility of boron nitride precipitation. Data available in the literature on the activity coefficient of solute boron in iron-base melts are inadequate for the present purpose. They will be reviewed briefly, however, so that comparison can be made, when

Jan 1, 1968

By G. Sachs

THE iron-rich iron-nickel alloys have at-tracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are Atomic per cent nickel FIG. I. FIG. 2. FIG, I.-HONDA'S AND MERICA's IRON-NICKEL DIAGRAM, FIG. 2.-MARSH'S IRON-NICKEL CONSTITU-TIONAL DIAGRAM. the base of many alloys with various out-standing properties. The iron-nickel alloys, therefore, have been investigated exten-sively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,1 and will be discussed in some detail in the sec-tions of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis,2 which is not dependent upon

Jan 1, 1940

By James Johnston

Synopsis.—A description of the working of the mills of this company and the metallurgical practice in vogue, by which a remarkably complex silver ore, averaging 54 oz. of silver per ton (run-of-mine ore), is treated to give a 95.66 per cent. extraction. The main features of the processes are: The cyanide amalgamation of the high-grade ore. The cyanide treatment of the low-grade ore, after extremely fine grinding and close classification, in a caustic soda solution. The use of a wet desulphurizing process to break up refractory silver minerals. The substitution of aluminum dust for zinc dust as a precipitant. The recovery and shipment of over 13,000,000 oz. of silver in bullion at 997 to 999 fine since this metallurgy was inaugurated, about 2.5 years ago. On the completion and successful operation of the mill to treat their high-grade ore,' the Nipissing Mining Co., under the general management of R. B. Watson, started a series of investigations of the possible treatment of the low-grade ore by the cyanide process, so that they would be in a position to market only silver bullion. These tests were run in July, 1911, on a large scale, by G. H. Clevenger, on an average mixture of Nipissing ore. The results obtained by a partiai amalgamation followed by cyanide treatment gave an extraction varying from 90 to 93 per cent. and were sufficiently encouraging to warrant Charles Butters, the company's Consulting Metallurgist, in recommending that the new low-grade ore mill under contemplation should be a cyanide mill, instead of a concentrator. The cost of such a mill, capable of treating 200 tons per day, to obtain a 90 per cent. extraction at a working cost of $3 per ton of ore treated, was estimated at $250,000. In coming to a decision as to which type of mill should be erected, the concentrator, with the subsequent shipping of concentrates to a smeltery,

Jan 1, 1915

By Haim H. Chiswik, Ralph Hultgren

In recent years considerable attention has been devoted to the development of new commercial uses for silver, chiefly because of lowered prices and large stocks of the metal. This has led to increased interest in the phase diagrams of silver alloys. The silver-lead diagram is reported' to be of the simple eutectie type, but no measurements of the solubility of lead in silver have been made. The solubility of silver in lead has been estimated2 from diffusion experiments and resistance measurements to vary with temperature from 0.09 to 0.18 atomic per cent (0.05 to 0.10 weight per cent). Silver-rich silver-lead alloys have recently been recommended as high-strength bearing metals3 The silver-bismuth diagram is similar.' The solubility of bismuth in silver. has been estimated to be about 5.5 weight per cent on the basis of X-ray work.4 Matthiessen6 found a solubility of silver in bismuth from 0.25 to 0.50 per cent by conductivity measurements. Silver and thallium form the same type of diagram,' with no data on their mutual miscibilities. We have studied the first two of these diagrams by X-ray methods, verifying their main features and determining the solubilities of lead and bismuth in silver at several temperatures. We also determined the solubility of thallium in silver at one temperature. The solubilities of silver in lead and in bismuth were found to be too low to be detectable. Materials and Methods Mallinckrodt precipitated silver, analytical reagent, was used. Maximum impurities listed on the label were: chloride, 0.005 per cent; copper, 0.001; iron, 0.002; other heavy metals (as Pb), 0.002; and sulphate (SO³), 0.05. The lattice constant was found to be a0 = 4.0782 $., in good agreement with the value of Jette and Foote,6 a0 = 4.0779 A., for

Jan 1, 1940

By Ralph Hultgren, Haim H. Chiswik

In recent years considerable attention has been devoted to the development of new commercial uses for silver, chiefly because of lowered prices and large stocks of the metal. This has led to increased interest in the phase diagrams of silver alloys. The silver-lead diagram is reported' to be of the simple eutectie type, but no measurements of the solubility of lead in silver have been made. The solubility of silver in lead has been estimated2 from diffusion experiments and resistance measurements to vary with temperature from 0.09 to 0.18 atomic per cent (0.05 to 0.10 weight per cent). Silver-rich silver-lead alloys have recently been recommended as high-strength bearing metals3 The silver-bismuth diagram is similar.' The solubility of bismuth in silver. has been estimated to be about 5.5 weight per cent on the basis of X-ray work.4 Matthiessen6 found a solubility of silver in bismuth from 0.25 to 0.50 per cent by conductivity measurements. Silver and thallium form the same type of diagram,' with no data on their mutual miscibilities. We have studied the first two of these diagrams by X-ray methods, verifying their main features and determining the solubilities of lead and bismuth in silver at several temperatures. We also determined the solubility of thallium in silver at one temperature. The solubilities of silver in lead and in bismuth were found to be too low to be detectable. Materials and Methods Mallinckrodt precipitated silver, analytical reagent, was used. Maximum impurities listed on the label were: chloride, 0.005 per cent; copper, 0.001; iron, 0.002; other heavy metals (as Pb), 0.002; and sulphate (SO³), 0.05. The lattice constant was found to be a0 = 4.0782 $., in good agreement with the value of Jette and Foote,6 a0 = 4.0779 A., for

Jan 1, 1940

By L. C. Kern

This paper presents information on the use of a new propping agent (malleable aluminum particles) which has been used successfully for producing high-conductivity fractures. The conductivity of a packed fracture depends on the width of the fracture as well as the permeability of the propping material. It is significant that the flow capacity of a propped crack is often increased many fold by propping the crack with a sparse distribution of particles. However, the flow capacity of a sparsely propped crack can be limited by two phenomena: (I) crushing of the propping particles, and (2) embedment of the propping particles in the formation walls. Malleable aluminum particles exhibit interesting properties which tend to overcome these limitations. As high loads are applied to the particles they will deform slightly, rather than shattering. The deformation results in a greater bearing area against the formation wall. This reduces the stress on the particle and reduces particle penetration into the formation. The behavior of aluminum particles under load and the bearing capacities of serveral formation rocks have been measured in the laboratory. By properly using these data, as explained in this paper, the flow capacities of aluminum-propped cracks can be calculated for a variety of conditions. Aluminum particles have been used successfully in the field to prop fractures. Where high-conductivity fractures were needed, the aluminum-propped fractures have given greater well stimulation than could have been expected for conventional fracturing processes. INTRODUCTION The purpose of a hydraulic fracture treatment is to create a conductive channel from the wellbore out into the oil or gas formation. The word conductive is emphasized because we believe that the fracture conductivity (flow capacity) is one of the most important factors influencing fracturing results. Previous papers have pointed out the additional well stimulation that can sometimes be achieved by increasing fracture conductivity. Several years ago, we investigated in some detail the effect of fracture conductivity on productivity increases to be expeced from vertical fractures. Both electrical analog and theoretical studies of unsteady-state flow behavior were made. A discussion of the electrical analog equipment and some of the results of the study were given in a previous paper' by Dyes, Kemp and Caudle. Further details were given recently by McGuire and Sikora.5 Fig. 1 shows the remarkable influence of relative fracture flow capacity and length on well stimulation. Briefly, the study indicates the following. 1. High-permeability formations require high-conductivity cracks for best results. 2. The longer the crack, the higher the fracture conductivity required for best results. 3. If the conductivity of the crack is very large compared to the formation (i.e., flow is not being limited by crack conductivity), then the longer the fracture, the better will be the results. Judging from recently published articles,1,314 there is current interest in methods for obtaining high fracture conductivities. Hence, we would like to present in this paper a discussion of a new fracture propping process (use of aluminum particle) which we have used successfully to obtain highly conductive fractures. There are several factors which influence the conductivity of a propped crack. Conventional fracturing techniques frequently result in a crack completely packed with fracturing sand. For such conditions, the crack conductivity is the product of the width of the packed fracture and the permeability of the propping material. It is significant that a large increase in conductivity sometimes can be obtained by propping with particles which are distributed sparsely (less than a

By Donald A. Brobst

The minerals barite (BaSO4) and witherite (BaCO3) are the chief sources of the element barium and its compounds needed for many industrial processes and products. Barite, the principal ore mineral, is found the world over and is abundant and widely distributed throughout the United States.3 Witherite is much less common than barite, though more desirable in many ways as a raw material for the production of barium chemicals. England is the chief producer of witherite. Witherite is not mined in the United States at the present time, but it has been mined with barite from a deposit at El Portal, California. Barite is also called barytes, tiff, cawk, or heavy spar. Ordinarily it is a heavy mineral that crystallizes in the orthorhombic system. It is colorless, white, or gray, and transparent to opaque. In some deposits barite is black, yellow, brown, red, green, or blue because of included impurities. The streak is white and the luster vitreous to resinous or pearly. The specific gravity of pure barite (65.7 pct BaO and 34.3 pct SO3) is calculated to be 4.5, but inclusions and impurities in natural barite may reduce this value considerably. Well-formed crystals are generally tabular and have three cleavages. The barite of many deposits, however, has an uneven fracture and an apparent cleavage caused by separation along planes between successively deposited layers. The hardness is 2.5 to 3.5 on Mohs' scale. Commercially the terms "hard" and "soft" are used to refer to ease of grinding. Barite is relatively insoluble in water and acid, and thus can be used as a chemically inert material. Witherite, the natural carbonate of barium (77.7 pct BaO and 22.3 pct CO2), crystallizes in the orthorhombic system. The fracture is uneven and the luster is vitreous to resinous. The hardness is 3 to 3.5. The specific gravity of the pure mineral is calculated to be 4.29. It is transparent to opaque. The color is ordinarily white, gray, yellow, brown, or green. Geology and Distribution of Deposits Workable deposits of barite are widely distributed throughout the world in many geologic environments in sedimentary, igneous, and metamorphic rocks. Most deposits can be classified into three main types: (1) vein and cavityfilling deposits; (2) bedded deposits; and (3) residual deposits. 1. Vein and cavity-filling deposits are those in which barite and associated minerals occur along faults, gashes, joints, and bedding planes, and in breccia zones and solution channels. They also occur in various collapse and sink structures in limestone. Sharp contacts of the veins and cavity fillings with wall rocks are common. Barite cements fault and collapse breccia by replacement of the matrix or by filling voids. Large-scale replacement of the wall rocks beyond ore-controlling structures is rare. Barite in vein and cavity filling deposits is generally dense, "hard," and white to gray. Associated minerals are fluorite, calcite, ankerite, dolomite, quartz, and many sulfide minerals, especially pyrite, chalcopyrite, galena, and sphalerite. Gold, silver, and rare earth minerals occur with barite in some deposits in the western United States. Barite is also a gangue mineral in metallic ore deposits but production as a byproduct from such deposits will be affected by many economic factors. The host rocks are igneous, sedimentary, and metamorphic rocks of pre-Cambrian to

Jan 1, 1960

R. 8. MACPHERRAN, Milwaukee, Wis. (communication to the Secretary): The importance of carbon in pig-iron, as well as the desirability of buying, for some purposes, irons which are high in carbon, has always been recognized. Mr. Summers, I think, has given undue weight to the carbon-determinations. The combined carbon often decreases materially as the center of the pig is approached, with a corresponding increase in the graphite. Even the determination of total carbon, to be of service, must he supplemented by that of other elements. By it alone, the softness of a foundry-iron cannot be determined. Car-wheels and No. 5 iron, for instance, frequently contain 3.75 per cent. of carbon. This is the percentage specified by Mr. Summers for his No. 1 iron, " with the silicon about anywhere the furnace-man wants it." It is true that, other things being equal, the higher the carbon the softer the iron for foundry-use. But to introduce any given percentages of graphitic and total carbon into a pig-iron specification would but make the specification more complicated, without increasing its value in a commensurate degree. Mr. Summers does not believe in the governing of mixtures by the silicon, and, in support of his views, gives several tables. It seems to me that both his conclusions and his tables are somewhat unsatisfactory. He comments on the irregularity in carbon, but fails to note the significance of the irregularity in silicon..The variation of 0.7 per cent. in silicon, for example, is too great to be accounted for by difference in blast. It might better be attributed to bad grading at the furnace, unsystematic sampling, or irregular charging. Deductions drawn under such conditions are of little value. In ordinary work the castings from the same mixture should

Jan 1, 1899

By Grimes, J. A.

EXTENSIVE discovery 'and rapid exploitation of orebodies within the past half century have attracted many able geologists to the mining industry and furnished them a wealth of data from which to develop theories concerning ore genesis. By tosting and elimillating theories which are not sufficiently sup- ported by fact, or which are based on inaccurate observation of field data, the trend of geological opinion has . moved strongly in certain directions until, at the present time, large numbers of geologists subscribe to a broad concept of .ore genesis that I would summarize as below:

Jan 1, 1928

By Leon W. Dupuy

Many articles have been written describing peculiar and particular types of drilling. Little correlation has been made between the character of ground to be drilled and sampled and the type of drilling most desirable for procuring satisfactory samples. In development work, the engineer and metallurgist often desire the recovery of a sample in as physically natural a condition as possible, particularly when the sample must provide material for process tests as well as chemical and physical analyses. This paper describes the results of experimentation in drilling unconsoli-dated materials carrying titanium minerals in the Magnet Cove area, Ark. The drilling was most difficult in that the ground varied much in consistency, and it was vitally necessary to recover a physically natural sample. Ordinary churn drilling recovered a sample that could be analyzed chemically, but the sample was not in its natural state. The problem was successfully solved by utilizing and further developing methods used in the oil and clay industries. In the Magnet Cove area of Hot Spring County, Ark., the titanium minerals include rutile, brookite, ana- tase, leucoxene, and others. They occur in soil, clays, and altered rocks adjacent to novaculite in contact meta-morphic deposits. In preparing titanium minerals for use in the industry, it is necessary to know the physical characteristics of the ore. Also it is believed that the particular physical character of the titanium mineral used is just as important as the chemical character. Brookite and rutile, for example, are the same chemically but differ in crystalline structure. In preparing titanium minerals for market, beneficia-tion is necessary. For the millman to make a satisfactory laboratory test, the sample he uses must be as nearly of the same physical character as he would have from mine run ore. In the past at Magnet Cove, churn drilling had been done on the properties, and assays of total titania had been obtained. It was found, however, that the total titania was indicative merely of the presence of titania but did not tell the metallurgist the character of the material or even give him the slightest indication of what he might expect to recover. When the Bureau of Mines entered the field in the winter of 1947 and 1948, it was therefore necessary that a natural sample be recovered. LIMITATlONS IN ORDINARY PRACTICE The churn drilling that had previously been done had shown that the occurrence of titanium-bearing mineral was somewhat widespread. The samples were, however, completely beaten up and in a finely powdered state. The minerals had been slimed, and such ore dressing tests as were made from the churn-drill samples were found to be worthless. Test pitting and outcrop sampling had provided satisfactory samples of surface ore but did not represent the entire ore body. A quantity of rutile had been produced from the surface residual concentrations in the westerly part of the cove, but production ran into metallurgical trouble as depth was attained. Representative deep samples upon which ore dressing research might depend were needed.

Jan 1, 1950

By George S. Rice

MANY studies on ground movement and subsidence have been carried on by members of the Institute during the past year, but only a few papers have reached maturity. Two of the mining schools of this country have continued their interest in ground movement research. At Columbia University School of Mines, Philip Bucky has continued his investigations, employing photoelastic methods and the use of his centrifugal apparatus for testing what he termed "the strength and behavior of mining structures." Helmut Landsberg, of The Pennsylvania State College, has developed a convergence recorder similar in principle to that used by the

Jan 1, 1936

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By Arthur Zentner

The electrolytic zinc plant of today is foreshadowed in the patents issued to Léon Létrange of Paris in 1881 and 1883l. He proposed roasting zinc blende to make the zinc soluble in water or sulphuric acid, thus obtaining a sulphate solution. His purification was apparently that used in the lithopone work of the day. For electrolyzing he proposed anodes of carbon or lead, for cathodes zinc, copper or brass. Numerous patents by other workers were taken out in the first 10 years, most of which dealt with sulphate solutions. It is easy to presume that the formation of chlorine gas in zinc chloride electrolysis caused early emphasis on sulphate work. Lack of success with this invited further work with chloride solutions. Efficient and cheaper oxidizing agents for use in the chloride processes were more generally available. Carbon anodes could be used instead of lead anodes, which were blamed for much of the early electrolyzing troubles and remained in disfavor for many years. Carl Hoepfner received his first zinc patents in 18902. He was the most persistent of those who worked with chloride solutions and met with the largest measure of success. Hc built three plants, only one of which remained in operation. This was built in 1896 at the plant of Brunner, Mond & Co., Winnington, England, now part of Imperial Chemical Industries Ltd. It leached with by-product calcium chloride from the company's Solvay alkali plant and returned to it the chlorine formed in electrolyzing. The zinc plant had a capacity of 5 long tons of zinc, said to have been doubled later, and remained in operation until 1924. No commercial plant using chloride solutions has operated since then. E. A. Ashcroft experimented in the middle nineties with chloride, alkaline and sulphate solutions on materials from Broken Hill, Australia. He built a plant with a rated capacity of 10 long tons of zinc per day, at Cockle Creek, New South Wales, in 1898. This figure was never approached nor was cyclical operation achieved. The work in the plant appears to have been largely with sulphate solutions. The plant suffered from a multitude of troubles: poor roasting, gclatinous silica, liberal use of live steam in solutions to combat the gclatinous silica with considerable

Jan 1, 1937

Alfred E. Hunt, Pittsburgh, Pa. (communication to the Secretary): Mr. Blue's statement (page 576) that, " owing to the presence of iron and other impurities, makers of aluminum. assert that native corundum is unsuited for the production of that metal," is somewhat incorrect, at least so far as it may refer to any objection made by the officials of the Pittsburgh Reduction Co. to the Canadian corundums. We recognize corundum as among the richest and purest of the ores of aluminum, and the material furnished from Canada would offer for us the advantage of a supply near to our works for the manufacture of aluminum at Niagara Falls. The real difficulty which we find in the use of corundum for this manufacture is the cost of the raw material as compared with that of native bauxites. In this item we include not only, the price of the corundum as it has been offered to us, but also the expense of grinding it to an impalpable powder, which must be done before it can be used directly in the manufacture of aluminum, and the cost of preliminary chemical treatment for purification—which latter operation, however, is also required for bauxite. I agree with Mr. Blue that the introduction of new and irnproved processes has greatly reduced, during the past ten years, the cost of manufacturing aluminum; but I am inclined to believe that any further improvements, facilitating the use of corundum for this purpose, would apply, in equal or greater degree, to the common clays (silicates of aluminum) which exist in all parts of the world, are more easily mined and handled, and are likely to be always cheaper per unit of aluminum than any corundum.

Jan 1, 1899