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By W. R. Ingalls

In reviewing the history of the metallurgy of zinc, I shall pass hastily over what is only of antiquarian interest. That has been excellently treated by Dr. Bernhard Neumann in "Die Metalle" (1904) and has been described briefly in my "Production and Properties of Zinc" (1902), in my "Lead and Zinc in the United States " (1908), and in other metallurgical works of more or less the same date. In this present monograph, I have it in mind to confine myself mainly to technical practice, especially to that of the last 75 years, prior to which period advance was slow and of no great moment. The ancients made brass by the cementation process, i.e., embedding copper in a mixture of calamine and carbon and heating, whereby zinc oxide was reduced and zinc was vaporized and combined with the copper. Zinc was isolated by some of the alchemists, who named it and knew something of its properties, but made no use of it. Long before then, however, zinc was produced in India. Later it was produced in southern China. Possibly the Chinese obtained their knowledge from India. The Chinese in remote places still produce small quantities of zinc. I have seen photographs of their furnaces; or pots, for they hardly deserve the dignity of being called furnaces. I imagine that they are the same that were used centuries ago, for I cannot conceive of anything more primitive. Anyway, it is certain that the idea of a commercial production of zinc in Europe was imported from the Orient, where the metal was known in commerce as Speauter and Spiauter, whence speltrum and finally our term spelter. Tutanego and Tuteneague are other old names. Dr. Isaac Lawson went to China about 1730, expressly to discover the method of its production. What connection there was between Isaac Lawson and John Champion we do not know, but the latter obtained in 1739 a patent for a process of distillation downward and at some time between 1740 and 1743 erected a works at Bristol and actually began the manufacture of spelter. A production of 200 tons per annum is mentioned. In about the year 1766, Rishop Watson visited the Champion works and saw the process in operation, which previously had been

Jan 1, 1937

By Howard Smith

AT the meeting of this Institute in February 1933, I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey's 20-year search for commercial sources of soluble potash minerals and of the events, that led to the discovery, exploration, and first development of the deposits in that state. As a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by. G: R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area .of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K20; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1935

By E. L. Jr. Spain

This study was undertaken primarily to determine the reasons for certain varia-tions in the soundness of gravel aggregate taken from a number of widely separated points on the Tennessee River. Under laboratory tests, concrete made with these various aggregates it some cases exhibited marked differences in specific gravity, crushing strength and durability. Gravel was studied in detail from Chattanooga to the mouth of the river and to a lesser extent from Chattanooga to Knoxville. The causes of variation were determined, and variational curves were constructed, which accurately predict the composition of aggregate at any point on the river and therefore its relative suitability for use in concrete. The aggregate at any point is suited for making sound concrete; the variance of suitability is due to varying percentages of sandstone and weathered material, which are less sound than other constituents. INTRODUCTION When it is stated that the aggregate from one point is inferior to that from another, it must not be construed to mean that the gravel is unfit for use. The classification upon which such aggregate ratings are based is largely arbitrary, thus inferiority or superiority is merely relative. Samples of gravel were selected from stockpiles at the dams of the Tennessee Valley Authority under construction, from the stockpiles of private companies along the river, and from samples taken by the gravel-exploration barge of the T. V. A. One hundred or more gravels of each size studied were selected at random by taking small handfulls while walking around the piles. These were separated according to the differ-ent mineral or rock constituents present, and the percentage of each constituent was obtained by counting. At least three such samples were taken from each size, and all checked with one another within a few per cent. The results were then averaged. In order to check on the accu-racy of such sampling, a whole sample was taken from one point after the gravel was thoroughly mixed. The two methods gave approximately identical results.

Jan 1, 1937

By F. E. Wood, H. W. Young, A. W. Buell

This paper summarizes the results of laboratory tests conducted to determine the properties of the paraffin or rod-wax encountered in the Salt Creek field, Wyoming. It also describes field tests and methods employed to cope with the paraffin problem. The conclusions to bo drawn from the laboratory work are: 1. Samples of Salt Creek paraffin range in consistency from soft lo hard, the melting points varying from 120" to 156" V. 2. Masses of soft paraffin are soluble to an appreciable extent in crude oil and its liquid fractions at temperatures somewhat below the melting point of the paraffin. Hard paraffin is very slightly soluble. under these conditions. 3. Agitation apparently increases the amount of paraffin that will go into solution. 4. Paraffin congeals from solutions upon cooling to the point of saturation ation, which is in all cnscs below thc melting point of the paraffin. 5. Crutltl oil is tlie most effective. of all the solvents for holding paraffin in solution. 6. Pressure alone does not appreciably affect the solubility of paraffin in crude oil nor does it aid materially in holding paraffin in solution when the temperature is reduced. 7. Natural gas in solution under pressure does not appreciably increase the solubility of paraffin in crude oil, hut is effective in holding paraffin in solution when the temperature is reduced. 8. A foreign body introduced into a solution of paraffin in oil is imrnediately coated with paraffin if the temperature of the solution is at or below the melting point of the paraffin, and the object is considerably cooler than the solution. It may not be entirely correct to ray that paraffin is taken into solution; it is impossible that the paraffin may be in suspension rather than in solution.

Jan 1, 1928

By B. F. Oliver

A levitation zone melter is described which has the necessary characteristics for processing metals of controlled purity. No crucible is required; control of the solidification variables is stable; the environment of the charge is chenzically controlled. Rotation of the solidifying interface and mixing in the liquid by the magnetohydrodynamic stirring produce an eight-fold increase in freezing velocity over former melting units with better resulting solute redistributions. The smooth appearance of processed specimens, resistivity ratios as a hnction of position, as well as a segregation curve, are presented as evidence of smooth continuous solute fransport over distances in excess of ten zone lengths. THE difficulties of the floating zone-purification of higher density metals in large quantities under conditions of lowered surface tension are well known and have hindered fundamental research programs for some time. The inordinate amount of time required to obtain a small reproducible yield of high-quality metal has excluded the use of such material for many important material research programs. However, with the use of controllable induction levitation forces' to accomplish stable liquid zones with nearly flat solidifying interfaces, and with good physical and chemical control of the processes involved, these difficulties can be overcome. A zone melter that is to be used for both high-purity and controlled composition work in metal systems must have the following three characteristics: 1) The process must avoid the use of containers. 2) Physical control of the solid-liquid interface and of the mixing within the liquid phase must be stable. 3) The chemical environment of the melt chamber must be controllable. A description of an apparatus that accomplishes these objectives follows.* APPARATUS One of the basic features that is necessary for good process control of large sections is that the charge, the coil, and the motion mechanisms be within the same chamber. This arrangement permits a close coupling between the work coil and the load, which then provides a good flexibility for adjustments of coil dimensions, for controlling the amount of levitation needed for stable operation at a given power level. An overall view of the melter is shown, with the melt-chamber door open, in Fig. 1. The radiation shields surrounding the single-turn induction coil are of water-cooled copper. The chamber is stainless steel, as are most of the components within the chamber. The control panel for the scanner is located at the immediate lower right of the melt chamber. This panel controls the operation of the scanner. The operations controlled are the interface rotation rate, the stretch-squeeze or diameter control, the up and down scanning speeds, and the induction power. All of the drive motors are constant-torque variable-speed motors. The scanning speeds are set with precision helipots and continuously observed with the voltmeter on the control panel and checked with a mechanical indicator within the melt chamber. The rotation rate is also set with a precision helipot. The up-scanning speeds are 2 to 300 in. per hr.

Jan 1, 1963

By E. L. Bruce

Gold occurs in many mineral deposits in the rocks of the Canadian Shield. It is present in the ores of many base metals and a considerable quantity is recovered as a by-product from the production of copper at Noranda, of nickel and copper at Sudbury and of copper and zinc at Flinflon. But the greater part of the gold production of Canada is from deposits in which gold is the only metal of value. No gold is obtained from placer deposits within the borders of the Canadian Shield. A brief review of the geological relations of some of the gold deposits of the Canadian Shield will be presented in an attempt to explain certain associations. Only those which are being worked for their gold content will be considered and descriptions will be confined to representative types of deposits, chiefly those of major importance; a few others, differing in certain features from those of the older and larger mines, will be included in order to illustrate the general conditions in which gold occurs in these ancient rocks. Brief summaries will be given of the geological relations of the Beattie and Siscoe mines of northern Quebec, of the mines of the Porcupine and Kirkland Lake areas of northeastern Ontario and of the Howey, Central Patricia and Little Long Lac mines of northwestern Ontario. Genetic relations to igneous rocks of granitic composition, outcropping in the vicinity, have been assumed for many of these deposits. Undoubtedly the ore minerals have been derived from igneous sources and, for some occurrences, there is evidence suggestive of genetic relationship between the ore bodies and neighbouring intrusive rocks. During the past few years, however, many investigators have expressed doubt of the genetic relationship of certain ore bodies to igneous masses near which they occur. As will be seen from .references in the following descriptions the importance of the structural conditions in localizing deposition has been realized. This is pointed out for Canadian pre-Cambrian gold deposits by E. T. Dougherty, who also refers to the

Jan 1, 1937

By Y. Oinouye, H. Ries

Of the several interesting physical properties of clay which have claimed the attention of investigators in recent years, none is more important than the behavior of the material when heated to temperatures above those of dehydration. Some of the problems to be solved are: 1. The mineralogical changes that take place in firing. 2. The relation between temperature and change in constitution, shrinkage, porosity, etc. 3. The importance of the time factor, as duration of firing, either in reaching a given temperature, or of exposure to a constant temperature. Mineralogical Changes As a result of fusion, reactions take place between the constituents of a clay, which result in a reorganization of the mass, and the formation of new compounds. Of the new minerals developed, sillimanite is the one usually recorded, and has been referred to by a number of observers.' There appears to be a difference of opinion, however, regarding the temperature at which it is formed. Thus Klein2 notes that sillimanite forms only above 1300" C., while Mellor claims that it can develop below 1200" C., the difference in results being conditioned by the time factor. In Klein's experiments the test pieces were fired in 12 hr., while in Mel-lor's, the temperature rose from 800" to 1180" in 24 hr., and occupied the same time in cooling back to 800".

Jan 1, 1918

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of ternary and quaternary additions of aluminum, oxygen, and carbon on the mechanical properties of high-purity titanium-molybdenum alloys were studied for several microstructural conditions. Heat treatments were designed to produce 1) ß-quenched, 2) equiaxed ß) transformed (acicular) and 4) stabilized -P microstructures. Tension, impact, and hardness tests were performed. Transformations from the ß phase were followed by hardness measurements and metallography. The ß-to-w transformation was slowed by aluminum additions; carbon and oxygen additions increased the transformation rate. In addition to solid-solution strengthening, these solutes may increase or decrease strength by altering the /3 transformation kinetics. Aluminum additions promote the formation of strain-induced martensite, and lower yield strengths at compositions near 12 pct molybdenum.. a-P alloys are more ductile with equiaxed than with transformed microstructures. High strength levels can be reached by aging in many cases. Strength levels of the aged specimens usually are lowered slightly by straining prior to aging. ALLOYS of molybdenum with titanium form an iso-morphous alloy system which has been the subject of several investigations. Additions of substitu-tional and interstitial -stabilizing elements provide means of improving mechanical strength and con- trolling the heat-treatment response of the binary alloys. The work reported here forms a part of a continued study of the effects of microstructure on the mechanical properties of high-purity titanium alloys. Previous papers have considered the various binary alloys (Ti-Mo, Ti-Al, Ti-C, and Ti-0) that form the bases for the ternary and quaternary alloys included here. The compositions were selected to correspond with the previous binary alloys. Further, the high purity of the alloying components was maintained, so that direct comparisons with earlier work can be made. The total research program included a large number of compositional, microstructural, and testing variables. The data reported here have been selected to provide a reasonably complete and representative summary of the results. The reader is referred to the original Air Force Report for a complete tabulation of the results. EXPERIMENTAL PROCEDURES All the alloys used in this work were prepared from high-purity electrolytic titanium produced by the U.S. Bureau of Mines. A typical furnished analysis showed the following impurities in wt pct, balance This analysis is equivalent to that of iodide-refined titanium. In addition, hardness, tensile, and impact tests made using unalloyed electrolytic titanium showed it to have properties equivalent to those obtained with iodide titanium and suitable for these studies of high-purity base alloys.

Jan 1, 1962

By H. N. Thomson

(Butte Meeting, August, 1913.) GENERAL. THE Tooele plant. off the International Smelting & Refining Co. is situated at the mouth of Pine canyon, Tooele county, Utah. It is connected with the main line of the San Pedro, Los Angeles & Salt Lake railroad by the Tooele Valley. railway, and is about 7 miles from Tooele Junction. Fig,. 1 is a general view of the plant. The copper plant has been in operation since July, 1910, and the first blast furnace it the lead plant was blown in on Feb. 29, 1912. The location of the plant was selected on sloping ground with the idea of using gravity to the fullest extent and thus keeping labor at a minimum. Practically the entire plant is constructed of steel, reinforced concrete, and. brick.

Jan 7, 1913

By C. G. Goetzel

Until recently porous bronzes have found many applications for self-lubricating bearings in the automotive, electrical, household appliance and general machine industries. The bulk of an annual production of several million pounds of copper powder had gone into the manufacture of these articles, of which by now more than a billion are in service. However, the war has brought severe curtailment of these bearings because of the scarcity of the two main constituents, copper and tin. The development of substitute materials of equal or superior properties has led to a large-scale replacement by products made from iron powder. In spite of the diminished interest in powdered copper-tin alloys caused by this trend, it was believed worth while to investigate some mechanical properties of these materials as a reference base for substitutes. In addition, experiments using the hot-press method were incorporated to investigate possibilities of saving vital equipment or opening new fields of applications. It must be assumed that by this time the powder metallurgy process of making porous bronzes, a development that found its first industrial applications more than 10 years ago, is well known in engineering. The patent literature and bibliography is volu- minous, most publications referring to porous, self-lubricating bronzes, containing about 10 per cent tin and I to 5 per cent graphite, with porosities in the range of 25 to 35 per cent.l-7 The excellent antifriction properties of these bearings, caused by the uniform impregnation with oil, are dependent on the interconnection of the pores and the uniform distribution of the graphite inclusions. The sintering mechanism of porous bronze, with its structural changes during the transformation of the metal powder into the sintered bearing has been shown in colored photomicrographs by Hall.* Diffusion between copper and tin was found to begin within one minute, when tin-rich transitory phases were formed. After 25 min. a homogeneous matrix of alpha was reached for an alloy containing 9.5 per cent tin and 6 per cent graphite. Price, Williams and Garrand,9 studying certain metal powder combinations in which sintering is accompanied by the cementing action of a liquid phase, including a 90-10 bronze sintered at 925°C., have found that if the treatment is carried out within the liquidus and solidus temperature range of the system, a peculiar process of alternate solution and precipitation occurs. The particles of the major solid constituent are dissolved in the minor liquid phase, but thereafter are reprecipi-tated on certain nuclei, which develop into large grains, usually rounded.

Jan 1, 1945

By William Phillips

THE possible sources of potash salts in the United States have been considered from many points of view during the last several years, but it is only within the last two or three months that the situation has become acute. We import from Germany, the only source of large supply, more than $10,000,000 worth of potash salts annually, and this business has been badly crippled by the European war. If there was ever a time in our industrial existence when the necessity of providing for our own needs was more acute than it is now, we are not aware of it. One has only to study the price, lists of chemicals sent out by the large supply houses to see the change wrought within a very short time. Whether or no these prices are to maintain for a considerable time, no one can say; but it appears to be probable that we shall not see prices materially lower for a period of uncomfortable length, to say the least. It is not my purpose at this time to discuss the various sources of supply of potash salts that have been suggested or recommended. Some of them might afford a pleasing relief but all of them combined would not affect the situation seriously. If we are to have our own sources of potash salts, they will have to compare, in some efficient manner, with the sources upon which we have drawn during the last 20 or 30 years; i.e., they must exist-in minable quantities. It seems to me to be quite idle to speculate upon our domestic sources of potash if those sources are not of a character similar to those upon which we have so long depended. A few thousand or, perhaps,, a few hundred thousand dollars' worth of chemically derived 'potash may be produced under the stress of present conditions, but when we consider that each year demands more than $10,000,000 worth, we must look to underground sources; we must look to mines similar to the famous Stassfurt and Halle deposits. If we cannot mine potash salts, we shall have to do without them for a while.

Jan 2, 1915

By F. I. Grace, L. E. Murr

The mechanical responses and residual defect structures in 70/30 brass and type 304 stainless steel following explosive shock loading and cold reduction by rolling have been studied. A distinct relationship was observed to exist between the residual mechanical properties and micro structures observed by transmission electron microscopy. Shock-loaded brass deformed primarily by the formation of coplanar arrays of dislocations and stacking faults at lower pressures, and twin-faults (deformation twins and €-martensite bundles) at higher pressures (> 200 kbar). The micro -structures of cold-rolled brass were characterized by dense dislocation fields elongated in the rolling direction. Stainless steel was observed to deform by the formation of dense arrays of stacking faults at lower shock pressures and twin-faults at high shock pressures (>200 kbar). Lightly cold-rolled stainless steel deformed similar to low Pressure shock-loaded stainless steel, but transformed to a' martensite in heavily cold-rolled stainless steel. Discontinuous yielding was observed for the heavily cold-rolled stainless steel, and stress reluxution in the weyield region for cold-rolled and shock -loaded stainless steel was interpreted as an indication of the ability of twin-faults and stacking faults to act as effective barriers to dislocation motion. A simple model for the formation of the planar defects and a' martetnsite is presented based on the propagating of Shochley partial and half-partial dislocations. A considerable effort has been expended over the past decade in an attempt to elucidate the response of metallic-crystalline solids to the passage of a high velocity shock wave (e.g., smith,' Dieter,2 and zukas3). While it has been possible to obtain relevant information pertaining to the residual defect structures and mechanical properties, there have been few rigorous attempts to draw a direct comparison between these structures and properties. In addition, numerous investigators have recently observed the occurrence of deformation twinning in shock deformed fcc metals (e.g., Nolder and Thomas,4 and Johari and Thomas5), but little attempt has been made to elucidate the mechanisms of formation of these defects. Comparative data for metals deformed by shock-loading and the same metals deformed by more conventional modes of deformation such as cold-reduction by rolling is also generally lacking. The present investigation therefore has the following objectives: 1) to examine the mechanical properties of some explosively shock loaded and cold-rolled fcc metals of low stacking-fault energy as a function of their residual substructures; 2) to present a simple model for the formation twin-faults and related defect structures in the low stack-ing-fault energy materials of interest (70/30 brass, ySFg= 14 ergs per sq cm; and 304 stainless steel, ySF = 21 ergs per sq cm); 3) to make some deductions with regard to the residual characteristics of dislocation and planar defect substructures in cold rolled and shock loaded 70/30 brass and type 304 stainless steel. In particular, it was desirable to characterize the residual hardening effects of particular deformation substructures. I) EXPERIMENTAL PROCEDURE Sheet samples of 70/30 brass (0.005 and 0.15 in. thick; annealed at 659°C for 2 hr) and type 304 stainless steel (0.007 in. thick; annealed 0.25 hr at 1060°C) of nominal compositions shown in Table I were cold-rolled in one direction only to produce reductions in thickness of 15, 30, 45, 60, and 75 pct in the brass; and 5, 15, 25, 35, and 45 pct in the stainless steel. Identical sheet samples in the annealed (unrolled) state were subjected to plane compressive shock waves to various peak pressures ranging from 0 to 400 kbar in the brass and 0 to 425 kbar in the stainless steel; and with a constant peak pressure duration of approximately 2 microseconds. A detailed description of the shock loading technique has been given previously.6 Tensile specimens 1.0 in. in length and 0.125 in. in width were cut from the cold-rolled sheets (tensile axis parallel to the rolling direction), and the shock-loaded sheet specimens. Stress (load)-strain (elongation) measurements on the tensile specimens were made on a Tinius-Olsen load-compensating tensile tester using a strain rate of 2.7 x 10-3 sec-1. Tensile tests were repeated at least twice, giving essentially the same results. Stress relaxation measurements in the preyield region were also made using an initial strain rate of 5.4 x 10-4 sec-1. In addition to tensile and stress relaxation measurements, Vickers microhardness measurements were made on all samples. A total of 100 microhard-ness readings were obtained for each specimen following a light electropolish to ensure uniform surface conditions for all tests. The hardness averages ob-

Jan 1, 1970

By F. A. Crossley

The key to disagreements between Blackburn's findings and mine is the word equilibrium". My work attempted to define the equilibrium diagram of the titanium-rich end of the Ti-A1 system. It can readily be shown that Blackburn's conclusions are based primarily on the examination of structures substantially removed from equilibrium. The diagram presented in Fig. 16 is properly labeled a "phase diagram". However, it appears that Blackburn either does not understand or does not accept the difference between "phase diagram" and "equilibrium diagram" as defined in the Metals Handbook.17 The conflict lies not in Blackburn's data but in his interpretation of it, and his use of "transformation", "phase diagram", and "equilibrium diagram" as synonymous terms. I share his view that the light microscope is much inferior to the transmission electron microscope for the study of transformations; but this fact does not render the light microscope useless or untrustworthy. The difficulties experienced with the Ti-A1 system have not been due to the limitations of the light microscope, but rather to the extreme sluggishness in achieving equilibrium at temperatures below 1000° C. Were it not for the light microscope employed with polarized light, the twin phase syndrome' might still be unrecognized and, as a consequence, still adding to the confusion of Ti-A1 investigations. (Ref. 1 should read ... Contract No. N161-25952 ... vol. 236.) Other, more sophisticated techniques, including electron transmission, simply confirm the erroneous tentative conclusions drawn from observations of structures due to the twin-phase syndrome. By the standards of most of the investigations of the Ti-A1 systems, seven of the fifteen compositions investigated by Blackburn were seriously contaminated with oxygen. The writer has found that 0.1 wt pct 0 shifts the a + Ti3A1 boundary to 1 at. pct lower A1 content at 700°C. At constant aluminum content, this corresponds to a temperature shift of the boundary of +25°c.18 Blackburn advises that the first group of alloys contained 0.1 to 0.15 wt pct 0, bur he does say whether the analyses were performed on as-received material or on specimens in their final state of heat treatment. This is especially important considering the 20-mil-thick starting materials. If specimens had been annealed in the two-phase a + 6 region it would have provided an indication of the final degree of oxygen contamination since up to about 12 at. pct A1 the boundaries of this region are well-defined for low-oxygen alloys. Blackburn questions the capability of light microscopy in determining phase boundaries in the Ti-A1 system. I submit that the a/a + Ti3A1 boundary in Fig. 1 of Ref. 1 over the composition range from 10 to 18 at. pct A1 was determined by dilatometry and supported by electron diffraction. Specimens of alloys containing 8, 10, 12, and 14 at. pct A1 were aged at 550°C for 1000 hr (under stress of 5000 psi to accelerate the tendency to equilibrium) and then fractured in tension at room temperature. Collodion was applied to the as-fractured (unetched) surface and, when stripped, carried away particles identified by electron diffraction as Ti3A1. Perhaps Blackburn will explain why these electron diffraction data were ignored. At this time, a technique for revealing or indicating

Jan 1, 1969

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By Howard E. Kremers

Since the discovery of the first-known rare earth elements more than a century ago, these metals have always been of academic interest. It is not so well known, however, that a rather stable, respectably large industry based on rare earths and their related materials has been in operation for more than 60 years. Rare earths, of course, are the elements having atomic numbers 57 through 71--lanthanum through lutetium in the periodic table. The most important commercial members of this group are mixtures of the lower atomic-numbered rare earths, and cerium. Although yttrium is not a rare earth, it occurs with rare earths and its properties are so similar to them that. it must be included in a discussion of these elements. In addition, thorium is important to most producers of rare earths because their ores generally contain this element. Thorium extractive metallurgy and technology is closely related to rare earth chemistry due to the frequent similarity of properties.

Jan 4, 1962

By John T. Norton, R. E. Hiller

The tremendous increase in the use of metals that have been prcpared by the various cold-working processes during recent years has greatly stimulated the investigation of problems concerned with the fundamental nature of these processes. It has been observed in practice that different methods of bringing about the same dimension changes in a sample result in a rather wide range of properties. Cold working reduces the ductility of a metal, or what is perhaps more nearly correct, its "working capacity," and naturally the manufacturer wishes to produce an article that has as large a working capacity as possible, and to produce it with the smallest number of operations. It has also been known for some time that cold deformation produces a parallel alignment of the crystal grains of a metal, and that the type of this preferred orientation depends to some extent at least upon particular processes employed in the deformation. The present investigation has for its purpose the study of the relations between the various factors of a cold-working process and the preferred orientation of the metjal crystals resulting from this deformation. The work is chiefly confined to a study of cold-drawn seamless tubing. Preparation of Samples The tubing samples used in this investigation were made of steel having a carbon content of 0.10 to 0.20 per cent, and were drawn on a standard type of draw bench. In order to obtain the large reductions, the annealed stock was coated with lead, for purposes of lubrication. The reductions of area stated refer to reduction from the annealed condition without intermediate heat treatment. The cold work was done as nearly as possible at room temperature. The samples of wire and strip used for purposes of comparison were of steel of approximately the same carbon content and were prepared in the manner indicated. X-ray Method of Investigation The condition of preferred orientation in cold-worked samples is best investigated by the X-ray method that employs a small circular beam of * Assoriate Professor of Physics of Metals, Massachusetts Institute of Technology. t Graduate Student, Department of Metallurgy, Massarhusetts Institute of Technology.

Jan 1, 1932

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;&apos; and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.&apos; The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.&apos; who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By Claude H. P. Lupis, John F. Elliott

The classic Siez~erts&apos; technique has been employed to determine the solubility of oxygen in liquid pure silver and the effect on the oxygen solubility of solute metal additions to liquid silver. The results indicate that oxygen deviates slightly from Sieverts&apos; law in pure silver as = 3.9. Gold, platinum, md palladium decrease the solubility of oxygen in silver. First-order free energy, enthalpy, md entropy interaction coefficients are determined from the data. An important aspect in the establishment of the formalisms to be applied to represent the thermody-namic behavior of components of solutions is the accuracy of the experimentally determined thermody-namic properties. Wagner developed the first-order free energy interaction coefficient.&apos; Recent papers2&apos;3 extend the treatment formally to other thermodynamic properties and define the second- and higher-order interaction coefficients. A current communication4 considers in some depth the requirements and limitations imposed because of experimental error on the use of several formalisms now under active consideration in the field. This communication reports the results of an experimental study of the behavior of oxygen in liquid silver alloys that was carried out concurrently with the development of Refs. 2 and 3 with the hope of providing sufficiently precise information so that enthalpy and entropy interaction coefficients could be determined. THE EXPERIMENTS The Sieverts technique was employed using an improved design of the reaction bulb over that developed originally by Humbert5 and subsequently improved by pehlke6 and Weinstein.7 The Vycor reaction bulb as shown in Fig. 1 was air-cooled and contained a port for the thermocouple angling off to one side and a vertical port for connections to the gas supply and

Jan 1, 1969