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By H. G. Landua, Leah L. Naugle, H. H. Lowry

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By Leah L. Naugle, H. H. Lowry, H. G. Landua

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By W. L. Fink, H. C. Stumpf, L. A. Willey

VERY few studies of the aluminum-sodium system have been reported. Heycock and Neville1 were unable to detect any solubility of sodium in liquid aluminum. Mathewson2 prepared an equilibrium diagram consisting of two horizontal lines at the melting points of the two metals. He was unable to detect solubility at either end of the system. Scheuer3 first developed a method for the chemical determination of sodium in aluminum and then studied the solubility of sodium in liquid aluminum. His method involved heating aluminum with excess sodium under hydrogen until the two liquids were at equilibrium, chilling the melt, and analyzing the aluminum-rich layer. He reported the solubility to be 0.l0 pct sodium at 700°C, 0.115 pct at 750°C, and 0.128 pct at 800°C. This paper on the aluminum-sodium system is the twenty-first in a series from the Aluminum Research Laboratories describing equilibrium relations in aluminum alloy systems. MATERIALS The alloys for this investigation were prepared from electrolytically refined aluminum (99.99 pct) and sodium of reagent quality conforming to specifications of the American Chemical Society.4 Chemical analysis of the aluminum showed the following impurities: 0.002 pct Si, 0.002 pct Fe, 0.002 pct Cu, <0.001 pct Mn, 0.002 pct Mg and 0.001 pct Na. The sodium content of all alloys was determined by either chemical or spectrographic standard procedures5 No. IIA and No. SII respectively. DETERMINATION OF LIQUIDUS The boundary of the miscibility gap was determined by a modification of the method of Scheuer3 and of that used by Henry and Cordiano.6 As finally developed the method was as follows: A fused alumina crucible 25 mm id with 75 mm depth and 1.5 mm wall thickness was placed on the bottom of a container made from a 4-in. length of 1 ½ -in. iron pipe and pipe caps. The space around the sides of the crucible was filled with 40 mesh crystalline alundum. A charge of 60 g of aluminum and 10 to 15 g of sodium was placed in the crucible, the sodium first being trimmed and rinsed with iso-pentane to remove kerosene. The container was tightly capped, filled with argon (99.6 pct pure), and heated to the desired temperature (between 670 and 800°C). A positive pressure of argon (about 8 mm of mercury) was maintained through a small pipe to the upper cap. After soaking for from 2 to 5 hr, the container was quenched by directing a stream of water onto the base, so that solidification of the aluminum-rich layer was rapid and essentially unidirectional. Analyses were made on drillings taken from the bottom of the ingots after machining off the surface layers. Pre-

Jan 1, 1948

By A. Bleier, E. D. Goddard, R. D. Kulkarni

The influence of the collector structure on the amine (RNH2, R=alkyl) flotation of quartz has been systematically investigated using a modified Hallimond microflotation cell. This study focuses on the effect of varying chain length, branching in the alkyl group R, polyfunctionality of the collector molecule, and alkyl substitution on the nitrogen atom. In addition, adsorption at the solution/air interface and electrokinetic results for the solid/solution interface were employed to further elucidate the role ad the interrelation of the structural parameters in the flotation process. Estimates of an electrical double layer attractive energy between the bubble and the solid particle are made.

Jan 1, 1976

By A. E. Bellis, T. W. Hardy

The problem of heat treating high-speed steel becomes more and more important as the design of cutters becomes more and more complicated in increasing the efficiency of mechanical operatioqs. Hundreds of dollars are spent in the design and manufacture of milling cutters of special form for rapid production of duplicate or interchangeable parts, and then, as the heat treatment is faulty on the one hand, or scientifically executed on the other, the tool fails after a few operations, or its efficiency is greatly increased. The practical operation of giving these complicated tools the right temperature necessary to bring out the best cutting qualities, and at the same time bring-the tool out "clean," is a difficult one and calls for no small amount of skill. In order to be on the safe side the average tool hardener uses a temperature much too low to give the best results with the high-speed steel he uses. In the case of cutters which are finished to a given diameter before hardening, it is impossible to grind the tool after hardening, so that it is essential that the surface be protected from oxidizing or de-carbonizing. It is the aim of this paper to describe some experiments on hardening high-speed stee1, in which metallographic means were used to determine the correct hardening tempcratures. The accompanying table and plates show the results of hardening experiments on five different high-speed steels. The analyses for carbon, tungsten, chromium and vanadium of each steel are given in the accom- . panying table. Six specimens from the same bar of each kind of steel

Jan 1, 1917

By B. A. Cheadle, K. P. Steward

Axial tensile, ring tensile, closed end burst, and free end burst tests were done at room tempe.vature and 300°C on three batches of Zircaloy-2 sheathing zuith different textures. Knoop hardness tests were also done on all batches. The mechanical properties of the tubes were largely dependent on the percentages of cold work, but were also markedly affected by the textures, particularly with respect to deformation behavio&apos;r. The deformation behavior observed confirmed Picklesimer&apos;s predictions, zuhereas Knoop hardness results could be correlated with texture and yield strength anisotropy after the ,method of Wheeler and Ireland. From the mechanical properties, and from efjectiue strain values deterrlzined at the fractures using a photoqid technique, it zuas concluded that tubing witlz a single preferred orientation of radial basal poles best combines strength and ductility for any given deqee of cold work. THE mechanical properties required in collapsible Zircaloy-2 fuel sheathing for water-cooled power reactors are strength to resist wrinkling deformation by coolant pressure and ductility to accommodate a small amount of deformation in service without rupturing. Zircaloy-2 tubing during fabrication develops pre- ferred orientations of the a Zr grains due to aniso-tropic deformation behavior, and these textures markedly affect mechanical properties. Picklesimer&apos; had predicted the deformation behavior of tubes with various textures, but the texture required to provide the optimum strength and ductility for a given degree of cold work has not been reported. To investigate this problem, tests at three transverse to axial stress ratios were done at room temperature and 300°C on three batches of Zircaloy-2 tubing covering a wide range of textures and percentages of residual cold work. Knoop hardness values were also measured to correlate with preferred orientation and yield strength anisotropy after the method of Wheeler and relland.&apos; 1) MATERIAL For this investigation, three batches of tube-reduced tubing were chosen from the Zircaloy-2 sheathing produced for the Douglas Point Reactor. Individual tubes were 191/2 in. long, 0.600 in. OD, and 0.0165 in. nominal wall thickness. The identities of the batches, together with their textures, are shown in Table I. The tubes had the normal Zircaloy-2 composition3 of 1.5 wt pct Sn, 0.3 wt pct Fe, Ni, Cr combined with the following oxygen concentrations: Batch VII 1140 to 1390 ppm 0 Batch VIII 1400 to 1750 ppm 0 Batch IX 880 to 1320 ppm 0

Jan 1, 1968

By F. D. Patchen

Changes in the properties of partland cement upon the addition of fine-ground silica are discussed. Data were collected from formulations cured for periods up to 60 days at temperatures varying from 180" to 350°F. Compressive strengths, permeabilities and thickening times are compared. It is demonstrated that addition of find-ground silica in proper proportion results in a hydrated cement with superior properties above 230°F; i.e., early compressive strengths are higher and increase with additional curing, permeabilities are significantly lnrver and thickening times are increased. X-ray analysis of hydrated cement samples have been used to determine more fully the complex chemistry of these systems. Dicalcium silicate alpha-hydrate was found in all neat cements cured above 260°F. A 10 weight per cent silica addition produced a maximum amount of this phase. Xonotlite and tobermorite have been identified as hydration products at 320°F in systems containing 35 or more weight per cent silica. Formation of these components appears to be primarily responsible for the gain in strength and reduction of permeability observed after the addition of silica. INTRODUCTION For several years it has been recognized that loss of compressive strength occurs when portland cement is cured at a temperature above 250°F. This phenomenon has been called "strength retrogression". More recently it has been recognized that increased permeability usually is associated with decreased compressive strength at these temperatures. At curing temperatures above 300°F, these factors reach serious proportions. A compressive strength loss of 50 per cent between curing times of 24 hours and 14 days has been reported,&apos; and permeabilities as high as 10 md have been measured in neat cements cured at 320°F for seven days.&apos; Earlier investigators,&apos; although unsuccessful in eliminating strength retrogression, stated ". . . .it appears possible that by the proper selection of additives for cement, strength loss with age at high temperatures can be either eliminated or considerably lessened". One solution suggested was the use of a pozzolanic material, hydrated lime, and a retarder. Menze15 in 1934 discovered that portland cement containing finely divided silica possessed high compressive strengths when the curing temperature was 350°F. The use of such a composition is now an established practice in the manufacture of steam-cured cement blocks. It is reasonable to assume that the same beneficial effect can be used advantageously in high-temperature oilwell cementing operations. Ludwig first mentioned the use of sand for this purpose. Later, a portland cement containing moderate additions of silica flour and retarded with CMHEC, a cellulose derivative. was recommended for high-temperature application." These formulations have been successfully employed in the field."&apos;" This paper presents the results of a research program to test the efficacy of finely ground silica in increasing the compressive strength and reducing the permeability of oilwell cement compositions containing portland cement. Included also are X-ray diffraction patterns of powdered samples which have been used to determine some of the important chemical reactions occurring in these systems. LABORATORY PROCEDURES AND MATERIALS All compressive-strength test specimens were prepared and cured from a slurry in accordance with API RP 10B, with two modifications. A final curing pressure of 5,000 psi was maintained for a one- or three-day period; but, for further curing, pressures were reduced to the vapor pressure of water at the curing temperature. Also, the water content was varied in samples containing silica to maintain the slurry viscosity within a range of 5 to 15 poise as measured on a consistometer. Test specimens at 180°T were cured in a water bath at atmospheric pressure. At higher temperatures the specimens were cured in a steam-jacketed high-pressure curing vessel at 5,000 psi for a one- or three-day period. cubes cured for longer periods were removed from the pressure-curing vessel after 24 hours, sealed in small bombs containing water and placed in an aging oven.

By L. E. Mannion

Sodium carbonate (soda ash) is one of two principal commercial alkalis. Its principal competitor is sodium hydroxide. The use of sodium carbonate is recorded in ancient Egypt, where naturally occurring brines and solid salts provided impure soda for early glassmaking. Until the 19th century, soda ash (as well as potash) was recovered mainly by leaching wood or other plant ashes. In 18th-century Europe, for example, leaching seaweed ash with hot water produced a brown laundry lye. One of the better grades of this material was a Spanish product, barilla, which analyzed 24 to 30% Na2CO3 (Hou, 1942). The modern chemical industry was born in 1691 with the LeBlanc process for making sodium carbonate from salt, sulfuric acid, and lime. English industry used this process extensively in the 17th and 18th centuries. The next major advance was in 1863, when Ernst Solvay devised the ammonia-soda, or Solvay process. The first of many Solvay plants was built in 1874. These supplanted the LeBlanc method and dominated worldwide soda ash production until 1974, when mined sodium carbonate became predominant. Although considerably less important until recently, natural sodium carbonate deposits historically have supported small soda ash operations throughout the world. Shortages during World War II stimulated production of "natural" soda ash from such deposits, particularly at Searles Lake, CA and Lake Magadi, Kenya. More spectacularly, increased production from the vast trona deposits in Wyoming has virtually supplanted the Solvay process in the US. Principal producers of natural soda ash as well as the character of the source deposits are listed in Table 1. [ ]

Jan 1, 1983

By I. E. Rosenzweig

The problem considered in this paper is as follows: An arbitrary horizontally stratified area is given. The electrical properties of this area are characterized by a function p(z) (Fig. I), which shows the relationship between resistivity p of the soil and the depth z. For such general case the apparent resistivity p* will be computed, by earth-resistivity measurements carried out by any given configuration of electrodes. General solutions of this problem appear to be very important for interpretation of field results of resistivity measurements, concerning structural investigations. Such solutions have been given by many authors for the special case of a finite number of homogeneous layers (Fig. 2)lV4 as well as for the more general case of continuously ranging resistivities.5-8

Jan 1, 1940

By I. E. Rosenzweig

The problem considered in this paper is as follows: An arbitrary horizontally stratified area is given. The electrical properties of this area are characterized by a function p(z) (Fig. I), which shows the relationship between resistivity p of the soil and the depth z. For such general case the apparent resistivity p* will be computed, by earth-resistivity measurements carried out by any given configuration of electrodes. General solutions of this problem appear to be very important for interpretation of field results of resistivity measurements, concerning structural investigations. Such solutions have been given by many authors for the special case of a finite number of homogeneous layers (Fig. 2)lV4 as well as for the more general case of continuously ranging resistivities.5-8

Jan 1, 1940

By J. F. Martin, J. E. Friedline, L. M. Melnick, G. E. Pellissier

A method has been developed for determining gases in steel in which the gases are extracted by vacuum fusion and analyzed by mass spectrometry. This method is especially applicable for determining small amounts of oxygen and nitrogen. The lower limit of detection for both oxygen and nitrogen is 0.0001 pct with an average deviation of about 0.0001 pct for oxygen and 0.00008 pct for nitrogen. Hydrogen analyses by this method are in good agreement with analyses by vacuum tin-fusion. A complete analysis of all gases extracted from a steel sample can be accomplished in 40 min. It has long been known that certain of the gaseous elements exert particular effects on the physical and mechanical properties of steel. With the recent advent of new experimental steelmaking practices it is now possible to obtain steels with extremely low contents of such elements as oxygen and nitrogen. Present methods for determining these two gases are of insufficient sensitivity as applied to steels made by these newer practices, and therefore a new technique was considered necessary. A review of the literature showed that the conventional vacuum-fusion method1 was the procedure most suitable for modification to obtain a sensitive method for determining the gaseous elements present in steel simultaneously. However, for trace amounts of gases it is impractical to increase the sample size because of the physical limitations of the apparatus and the increased degassing time which would be necessary. Also, when only one of the desired gases is present in trace amounts, quantitative separation by conventional vacuum fusion is almost impossible. Since small analytical mass spectrometers are now commercially available, it was decided to use this instrument in conjunction with conventional vacuum fusion for both qualitative examination and quantitative determinations of the gaseous elements in steel. This technique has already been used with success for the analysis of copper and lanthanum.2"4 APPARATUS A vacuum-fusion unit was first designed and built, Fig. 1. This unit was designed especially for the determination of small amounts of nitrogen and/or oxygen in steel since an acceptable method (vacuum tin-fusion)5 was already in use for the determination of hydrogen in steel. The vacuum system was con- structed of Pyrex glass throughout. Mercury check valves were used in place of stopcocks in the high-vacuum section of the system. Ferromagnetic samples are normally introduced into the vacuum system through a mercury lift. In case of a break in the lift, the mercury is prevented from entering the furnace by a self-locking, mercury safety check valve, Fig. 2. This check valve, developed at our laboratory, is a modified T/S ball-and-socket joint placed in the sample inlet system between the mercury and the furnace. A sudden entry of mercury or air pushes this valve into the closed position, completely blocking the top of the mercury lift. The check valve is held in the closed position by the vacuum of the apparatus. A separate entrance tube also was placed in the system, so that samples which would amalgamate with mercury, or which are nonmagnetic, could be introduced into the furnace. A slightly modified Guldner-Beach furnace is used in this system.8 The optical flat was connected to the system by a ground-glass joint to facilitate cleaning, a quartz delivery tube was substituted for Pyrex, and the crucible was used uncovered. Fusion takes place in a high-purity graphite crucible insulated by — 200-mesh high-purity graphite powder. The crucible set (crucible and funnel) is suspended in a quartz crucible. The furnace envelope and the sample inlet system are exhausted by 2 single-stage, mercury-diffusion pumps in series. The first of these is a high-speed pump, which will work only with a very low backing pressure. This pump is used to exhaust the gases from the furnace as rapidly as possible. The second mercury-diffusion pump is used as a backing pump for the first; the capacity of this pump is much lower. However, it will work efficiently against a back pressure of 3 mm of mercury. To assure positive pumping, a modified Naughton and Uhlig condenser7 is used. With the use of proper valving the second pump is also used as a circulation pump in the catalyst system.

Jan 1, 1959

By W. L. Remick

WHEN the senior author of this paper presented an article on Fine Coal Cleaning by the Hydrotator Process,1 at the February, 1927, meeting, that process had been developed in the anthracite region only to clean what is known as "slush" or "silt." This size constitutes all of the material passing the finest screen used at any particular colliery. Some use a 3/32 -in. round-hole screen and others use a 1/16 -in. round hole. Practice varies throughout the anthracite region, but the tendency seems to be toward the finer screen.

Jan 1, 1929

By Reno Sales

THE present-day application of geological knowledge to mine opera-tions owes much to Survey activities. Early publications covering developed deposits at Comstock and Eureka in Nevada, and Leadville in Colorado, aroused great interest in mine geology among mine owners and operators. In later years personal contacts between Survey geologists, notably Lindgren, Spurr, Emmons, Weed, and Ransome, to name only a few, and mine managers, mine superintendents and mine foremen, brought directly home the importance of geological mapping and study in connection with mine operations. However, the Survey had recognized from the beginning that it was not practicable, either from the viewpoint of cost or policy, to supply direct help to the miner. The situation was met by many large mining companies through the organization of geological departments to deal with problems of geology which concerned not alone the every-day mine operation but also the life expectancy of the ore deposit. The mine owner therefore looked to the mine geologist to apply the "laws of ore deposition" in estimating the future of his mine. The examination of outside properties also became a duty of the company geologist where replacements were needed or where expansion of operations was contem-plated. And finally, out of this situation there developed the inde-pendent consulting geologist, specializing in geological examinations of prospects, mines, and mining districts, whose duties included the highly important but often difficult task of appraising ore reserves and ore possibilities. Thus, while it may be considered by many that the work of the mine geologist overlaps that of the Survey geologist, their respective fields of endeavor are not in conflict. The appearance of the mine geologist has lessened in no manner the need of intensive field and research work by the Geological Survey and related organizations.

Jan 1, 1934

By James Gayley

The atmosphere, which plays such an important part in the manufacture of iron and steel, is the most variable element involved in its several processes; and particularly is this true of the blast-furnace process, which consumes air in large quantitiee. At no time since the blast-furnace became an important and widely used apparatus—even when it was operated in the most crude manner—have the variations in composition of the raw materials used been as frequent and as great as the variations in humidity of the atmosphere. Important improvements have been made in the blast-furnace and its accessories, such as the hot-blast stoves, the increase in size and change in the shape of the furnace, more efficient blowing-engines, the increased protection given to the bosh-walls, and the careful preparation of the raw material, all of which have exerted a pronounced influence on the furnace-operations from a metallurgical standpoint. But during the past eight years little advance has been made in this direction; the fuel-consumption has not diminished, nor has there been any material increase in production. Within that period, however, there has been witnessed the greatest development in appliances for the economical handling of material. So complete has been the work in this direction, that, except in isolated cases, in this country at least, a further extension does not hold out much promise of a satisfactory return on the investment required. It seemed that, with the exception of the gas-engine, we had about reached the limit, for like a strong wall, the atmosphere, with its humidity as variable to-day as when first blown into a primitive blast-furnace, appeared to stand as a barrier to

Jan 1, 1905

By J. S., Douglas

IN 1880, the late James Douglas, LL.D., was superintendent of the Chemical Copper Co., operating the Hunt & Douglas process for the treatment of the siliceous copper ores of the Jones mine at Phoenixville, Pa. In conjunction with this a refining furnace was operated. After correspondence with Ben Williams, of Bisbee Ariz., who was commencing the mining and smelting of the Copper Queen ore. Dr. Douglas decided-to make his first journey to Arizona. While making plans for the trip lie visited a friend in Philadelphia, a .Mr. Logan, a prominent lawyer. He, through Professor Treadwell, brother of the discoverer of the great Treadwell gold mine of Douglas Island, Alaska, had an option with his min¬ing partner, Mr. Lenig, on the Eureka and Wade Hampton claims near the headwaters of the Verde River in Yavapai County, Arizona. These two claims, later the source of practically all of the wealth of the Jerome district, were then owned by C. P. Head and Co. Prescott merchants. Hugo Richards, banker, and formerly sutler at Camp Apache; Rod and John McKinnon prospectors and Nova Scotians; and perhaps one or two &apos;other owners of minor interests. Mr. Logan, hearing of Dr. Douglas intended trip to Bisbee, asked him to go first to see the two mining prospects, and this, Douglas, in need of the $500 fee, agreed to do as the time on the option on the claims was running short.

Jan 1, 1935

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnXTe have been grown from The melt under liquid B2O3 using the Czochralski technique. The PbTe-SnTe crystals were grown from near-stoichiometric melts and from melts with slight deviations from sloichiometry. Crystal growth rates ranging from 1 mm per hr to 1 cm per hr were employed, the latter being generally used. Several investigations were performed to characterize the single crystals grown In this study. The phase diagram of the PbTe-SnTe system was examined. X-ray analyses verified the single-crystal character of the crystals, and powder pattern lattice parameter determinations showed that Vegard&apos;s law was followed within the limits of the experimental error. The as-grown crystals were p-type with apparent carrier concentrations of -8 x 1018 to -8 x 1020 carriers per cu cm. Hall coefficients, resistivities, and carrier mobilities were determined as a function of composition. Dislocations were revealed by an electrolytic etch, and the crystals were found typically to contain 2 to 4 x 105 dislocations per sq cm. Microhardness measurements were performed; no maximum in the Vickers hardness us composition curve was seen. Mass spectrometry was used for impurity analyses, and the crystals were found to contain 1 to 2 x 1017 total p-type impurities per cubic centimeter. Distribution coefficients were calculated for the major impurities which were Na, Mg, Al, Si, Cl, and Zn. RECENTLY interest has been stimulated in the preparation and characterization of many alloys of the binary compound semiconductors. This interest is due primarily to the almost unlimited possibilities of adjusting the semiconducting characteristics of these materials by varying the alloy compositions. One alloy system which has been receiving extensive investigation is the PbTe-SnTe system, since these alloys show promise of being useful as emitters and detectors of electromagnetic radiation in the spectral range of 8 to 14 µ. This paper reports on the growth of PbTe-SnTe single crystals by the Czochralski technique and investigations of the general properties of these crystals. The phase diagram of the PbTe-SnTe system was investigated so that specific alloy compositions could be attained. I) CRYSTAL GROWTH The PbTe-SnTe single crystals were pulled from the melt using the Czochralski technique. Generally, the crystals were grown from near-stoichiometric melts, although special growth runs were made from both lead-rich and tellurium-rich melts. Growth of single crystals from up to 5 pct lead-rich melts presented no problems; however, melts with tellurium in excess of -1 pct caused volatilization problems which generally made crystal growth impossible. All melts were prepared from high-purity materials as follows: 1) lead— 6 N— Cominco (Cominco Products, Inc., Spokane, Wash.); 2) tin—5N—Cominco; and 3) tellurium— 5N+— American Smelting & Refining Co., Plainfield, N.J. No further purification of materials was undertaken in this study. The elements were reacted at -1000°C in a vacuum-sealed silica tube for a few hours, a gentle rocking action being used to ensure thorough reaction. The cast ingots were then transferred to a silica crucible for crystal growth. A schematic diagram of the growth apparatus is shown in Fig. 1. The Vycor tube is sealed at both ends by O-ring flanges so that a vacuum or a positive pressure may be maintained in the growth chamber. The pull rod and crucible may be rotated; all crystals produced in this study were grown with the crucible sta-

Jan 1, 1969

By Philip D. Wilson

SPEED is essentiaI in this war program and it is hard to keep up with developments. When the title of this paper was chosen, the contemplated magnesium production for which plants were then under construction was some 200,000 tons of metal per year or sixty times the 3350-ton production in prewar 1939. A few- days later an analysis of the President&apos;s 185,000-plane pro-gram, incendiary bomb schedules, and the additional requirements of the Army. Navy and Maritime Commission made it apparent that a much greater amount of magnesium must be provided in 1943. The new figures are huge but the censor will not per-mit their disclosure.

Jan 1, 1942

By J. W. Snavely

THE high tension belt conveyor is introducing a new and tremendously expanded era of low cost bulk material handling. High tension belt conveyors are generally those installations involving very long centers, high lifts, or drops, in which the belts are stressed up to their maximum tension values, and further, where the belt construction provides tension capacity far beyond what is possible with conventional belt constructions. With these high tension installations, the magnitude of the forces involved demands careful refinement of accepted design practice in order to achieve optimum balance of all factors. No attempt will be made to evaluate the relative merits of belt conveyor haulage with other means of transportation. For present purposes, it is assumed this has already been done in favor of belt conveyor. Neither will any attempt be made to evaluate the various conveyor belt constructions now available or to balance the advantages of various types of mechanical equipment. It is also assumed that the basic haulage information on which the conveyor design is based is accurate and complete. A sustained maximum, uniform load on the belt at all times must be achieved through proper feed control and the use of adequate surge storage to level the peaks and valleys of any varying demand for the material being handled. General Belt Capacity Considerations The belt conveyor capacity tables published by various belting and conveyor equipment manufacturers vary to a considerable degree, and the ratings given are quite conservative. Of necessity, these published ratings are based on the handling of average materials under average conditions. In applying a high tension belt, all possible capacity from the belt must be obtained in order to hold its width to a minimum and thereby limit the initial cost. Two factors are involved, loading to maximum cross section area and traveling at a maximum practical speed. Belt Loading: Proper treatment of the loading of the belt will result in maximum cross section to the load, and published capacity ratings can be exceeded, sometimes by appreciable margins. On the 10-mile conveyor haul used in the construction of Shasta Dam, California, although the rated capacity of the belt line was 1100 tons per hr, at times the system handled peak loads of 1400 tons per hr, almost 25 pct better than the rated capacity. One of the large coal companies has been able to exceed rated capacity by as much as 50 pct. Loading conditions which must be controlled are: 1. Large lumps must be scalped off and rejected or the load must be primary crushed before being placed on the belt. 2. The material weight per cubic foot must be accurate, must be known for all the materials being handled, and must be known for the complete range of conditions of the individual material being handled. Long centers and high lifts magnify small differences into serious proportions. 3. Uniform feeding to the belt is most important. Various types of feeders are available, which can be used to place a constant predetermined volume of material on the belt, or, where an appreciable range of material weight exists, through electrical control actuated by current demand, to place a predetermined uniform tonnage on the belt. One long slope belt in a coal mine in Pennsylvania is being fed at three separate stations with the controls so arranged that whenever the maximum load is going onto the belt from the first station, the other two stations automatically cut out. Whenever the load from the first station drops back, the other two stations again automatically cut in. 4. Careful design of the chutes and skirts is necessary to get the load centered on the belt with a minimum of free margin along each edge. Some free margin at the edge of the belt is necessary to prevent spillage, but if the load can be kept accurately centered, this free margin area can be reduced, and more material can be carried on the belt. What can be accomplished in this respect will vary widely, depending on the nature of the material being hauled. The chute and skirt design must also protect the belt. 5. The design of chutes and skirts should also get the load traveling in the same direction and close to belt speed, so that the load comes to rest on the belt as quickly as possible. The design of the chutes and skirts is worthy of careful study, and after a system is put into operation it should be experimented with to get the best results. Belt Speed: High belt speeds should be used in high tension work. Obviously, high belt speeds enable haulage on a narrower belt, reducing initial cost. The major portion of belt wear takes place at the loading point and around the terminal pulleys. The

Jan 1, 1952

By William L. Fink, L. A. Willey

Since so many different curves have been published for the solid solubility of zinc in aluminum, it seems desirable to definitely establish the correct curve by two or more independent methods. The curve published in part I1t was based entirely upon X-ray measurements because the other methods employed at that time were not satisfactory. The present paper (the seventeenth of this series on high-purity aluminum alloys) describes the determination of the solid solubility of zinc in aluminum by the measurement of electrical resistivity at temperature and by microscopic examination. Since the publication of our part I in 1932, an investigation of the solubility relations in the aluminum-zinc system has been reported by Schmid and Wassermann2, who obtained their solubility results from lattice-parameter measurements on heat-treated and quenched specimens. The diagram that they published is shown in Fig. 1. In this investigation they also found by X-ray measurements that the parameter of the gamma phase changed continuously with zinc content and at such a rate that it would be identical with that of the beta phase at 60 atomic per cent zinc. It was concluded therefore that the beta and gamma phases, from the point of view of structural relationship, are one single phase. They also suggested a gap of immiscibility between 270" and 350" C. The complete boundary in this region could not be determined satisfactorily by the method employed and therefore was not shown in their diagram. Aluminum-zinc Alloys Materials Used.—Electrolytically refined aluminum3 was used in preparing the alloys for the work reported in this paper. Chemical analysis showed the following impurities: 0.004 to 0.005 per cent silicon, 0.006 to 0.008 per cent iron and 0.005 to 0.006 per cent copper. Also,

Jan 1, 1936

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969