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By Andrew Mayer

Early in 1942 National Lead Co. was requested by the War Production Board to construct and operate a plant for the Government to produce magnesium by the ferrosilicon process which had been developed by Dr. E. M. Pidgeon in the laboratories of the Canadian National Research Council. A contract with the Defense PlantCorporation was concluded in May 1942 and Magnesium Reduction Co., a wholly owned subsidiary of National Lead Co., was formed to carry out this project. The capacity of the plant was rated at I0,000,000 lb. of magnesium per year, equivalent to an average production of about 14 tons per day. The Process The process, in brief, is as follows: The raw materials are dolomite and ferro-silicon, 75 per cent grade. The dolomite is calcined, the calcine and ferrosilicon are ground and mixed and the mixture is briquetted. The briquets are charged into tubular retorts of chrome-nickel steel set horizontally in a furnace with the open ends projecting outside the front wall. The retorts are then closed and evacuated. Magnesium is liberated according to then reaction 2(MgOl CaO) + Si = 2Mg + zCaO, Si% It is distilled from the charge and con- densed on a removable sleeve in the throat of the retort. Sodium and potassium, if present, are also liberated, distilled and condensed on a "sodium condenser" in the end of the retort. At the expiration of the distillation period the retorts are discharged and the cycle of operations is repeated. For the rated daily capacity of 14 tons of magnesium there are required approximately 170 tons of dolomite, equivalent to about 85 tons of calcine, and 16.5 tons of ferrosilicon. The retort residue, a bulky powder which at present is waste, amounts to about 87 tons. Choosing the Site The investigation to select the location of the plant was conducted by the Research Laboratories of National Lead Co. This work included geologic and economic surveys of a number of districts, examination of dolomite samples by chemical, spectrographic and petrographic methods and large-scale tests of dolomite from several of the more promising localities. in the last-named tests 2-ton samples were put through the ferrosilicon process in the pilot plant of the Canadian National Research Council, under the guidance of Dr. Pidgeon. The conclusions drawn from the investigation, in regard to the quality of dolomite to be used in the ferrosilicon process, were: First, the dolomite should contain not less than 21 per cent MgO and not more than 2 per cent acid-insoluble material. Second, the dolomite should

Jan 1, 1944

By L. W. Strock

Metallurgists handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. 'lore preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The howledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Expcrience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,' but the incentive has gradually changed since the summer 0. 1940 to the specific practical problem of searching for domestic sources of rare and stratcgic metals. The

Jan 1, 1949

By B. L. Averbach, M. Cohen

THE PROBLEM MANY hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or subatmospheric cooling.1,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1948

By Jr. W. L . Phillips

The deformation and fracture characteristics of lithium-fluoride single crystals stressed in compression at room temperature have been studied. In as-cleaved specimens the stress-strain curves were variable; two types of {110} fractures were observed in the vicinity of kink bands. The stress-strain curves of annealed crystals were reproducible; {100} cracks formed which propagated along the (100) and (110) planes. The deformation and fracture characteristics were affected by quenching and X-ray irradiation. STUDY of the mechanical behavior of nonmetallic materials has received considerable impetus in recent years because of the need to overcome the problem of brittleness before the refractory properties of nonmetallics can be fully exploited. Ionic crystals provide a convenient and simplified starting point from which to study the deformation and fracture processes in nonmetallic materials. Early investigations of the mechanical behavior of non-metals were restricted largely to determinations of the crystallographic indices of the cleavage and fracture planes and the glide and twinning elements. Until recently, only occasional systematic studies of the deformation characteristics of non-metals have been made; and investigations of the forces necessary to initiate plastic deformation and the factors which affect the flow characteristics have been restricted largely to studies of sodium chloride'-7 , magnesium oxides-l3 and lithium fluoride. 14-22 Fracture studies on alkali halide and metal oxide single crystals have been limited despite the fact that these materials have a number of advantages for fracture studies. Because they are transparent, the cracks which form can be viewed in three dimensions instead of in two dimensions as in metals. Also, they exhibit stress birefringence under polarized illumination, which enables the internal stress pattern and, therefore, the distribution of dislocations to be examined in the vicinity of the fracture. Early workers1-4 have shown that ionic crystals with a cubic structure fracture in tension along the (100) plane normal to the applied stress. These fractures were brittle at room temperature and propagated very rapidly across the cross section of the crystal. More recently, Stokes, Johnston, and Lil0 have studied crack formation in compressed magnesium-oxide single crystals. They found that the cracks, which were observed after about 3 pct strain, formed in the region of a kink band and lay on conjugate (110) slip planes instead of the usual(100) cleavage plane. Two different types of cracks were noted: stroh23 and secondary. The Stroh cracks did not exist merely on the surface but extended through the specimen in the form of tiny slits. A secondary

Jan 1, 1962

By W. Crafts, J. L. Lamont

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By J. L. Lamont, W. Crafts

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.' However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By O. Jay Myers

THE war effort has furnished the necessary impetus for better magnesium foundry practice. Four or five years ago, there were but a few formulas in general use for cores and mixtures for magnesium castings. Certain sands, binders, and inhibitors were specified and the proportions of these materials in each mixture were maintained between very narrow limits. As more and more war industries entered the field, much research was carried out and methods and practices were improved. Magnesium founding is still in a state of flux; therefore it is not uncommon to find one foundry spraying inhibitors on its cores, and another foundry using sand mixtures with incorporated protective agents. The basic core or dry-sand mold mixture for magnesium in use today is compounded with sand, core oil or resin binder, cereal, and moisture. Core oil or resin binder are added for baked strength while the cereal binder and moisture are for green strength. The normal mixtures (based on the weight of the sand) contain from 0.5 to 1.5 per cent of both cereal binder and core oil, and the moisture content varies between 1.5 and 5 per cent. The ratio of core oil to cereal binder varies from 60:40 to 40:60, while the correct amount of moisture depends upon the method of coremaking. PROTECTIVE AGENTS In all magnesium practice, protective agents are used in conjunction with the core and molding sands to prevent oxidation of the metal. The use of these inhibitors is not novel, but publications covering this field are not entirely adequate. Beck1 says Magnesium alloys decompose water to form magnesium oxide, hydrogen being liberated in the process (Mg + H20 -+ H21 + MgO). This reaction results in the blackening of the skin and the appearance of areas of porosity on the casting surface, the cavities of which are filled with a grey oxide powder (these are termed `burns'). Although sand cores for magnesium castings are thoroughly dried during the baking cycle, burning will take place on the castings unless the metal is protected properly. This type of burning is more difficult to define than the "water-magnesium" reaction cited by Beck. A possible explanation may lie in the following equation: 2Mg + 02 -s 2MgO Here, the source of the oxygen is not water, but the air in the mold cavity, together with the chemically combined oxygen in the core-binding media. Generally, two methods are used to prevent this reaction from taking place.

Jan 1, 1945

By d&apos, L. Berenbaum, F. Heurle, R. Rosenberg

The structure of aluminum films obtained by evaporation was studied by electron microscopy, mostly by replica techniques and X-ray diffraction. The resistivities and stress conditions of the films were also determined. Film properties were studied as a function of source selection, substrate type, residual pressures of oxygen and water vapor, substrate temperature, and rate of growth. The formation of abnormal localized growths and whiskers resulting from annealing treatment subsequent to deposition was investigated. Films deposited onto single-crystal substrates were found to be epitaxially 0riented; for such films, relative orientations between films and substrates were determined. ALTHOUGH wide use has been made of evaporated aluminum films for the formation of conducting lines on semiconductor devices, relatively little has been reported concerning the structural characteristics of such films.1"9 The purpose of this study was to obtain an overall view of the dependence of these characteristics on film deposition and subsequent annealing conditions, which were similar to those used in silicon planar technology. Accordingly, most of this study was carried out using oxidized and bare silicon wafers as substrates, although some work was also done using alkali halide, magnesium oxide, and mica substrates. However, the main concern remained pragmatic. Emphasis was given to the study of the effects of deposition and annealing conditions on film characteristics such as structure, resistivity, and stress. I) EXPERIMENTAL PROCEDURES The films which were investigated in this study were deposited in 18-in.-diam glass chambers which were connected to the usual type of trapped diffusion pumps filled with silicon oil. Through the use of liquid-nitrogen-cooled Meisner traps and titanium sublimation pumps placed inside the deposition chambers, the pressure could be lowered to the lower portion of the 10- I Torr range and little increase in pressure would occur during the deposition cycle. Unless described otherwise, the substrates were 1-in.-diam p-type silicon wafers having a resistivity of 10 ohm-cm. The wafers were oxidized in wet oxygen at 975°C followed by a short dry-oxygen exposure at the same tempertture to a total oxide thickness of approximately 6000A. The wafers, backed by a layer of gallium, were mounted onto molybdenum discs brazed to a copper block.10 The latter was heated by imbedded commercial cartridge heaters. The substrate temperature could be maintained to within +10°C of a prescribed temperature during film deposition. The search for a satisfactory source for the controlled evaporation of aluminum has led to the use of 1-in.-diam crucibles" machined from rods of a commercially available, refractory composite* of Bn and

Jan 1, 1969

By Michael Tenenbaum, C. C. Brown

Numerous investigatiolls have been carried out to determine the total oxygen present in the basic open-hearth bath and the results of these studies have clearly defined the factors controlling the bath oxidation during the period prior to deoxidation. On the other hand, very little is known concerning any changes in total oxygen content that may occur during deoxidation, tapping and teeming. The need for such additional data is continually becoming more apparent, since there is no strict technical basis for selecting any particular deoxidation practice. Many steels are made for the same purposes and to the same chemical analyses by widely differing practices. Apparently, each practice is satisfactory. However, it would be desirable to establish more definitely the effects and relative merits of the individual practices. Such information could be used to give a definite foundation for evaluating various types of deoxidation. In order to approach this problem, a study was made of the changes effected in the total oxygen content of several grades of steel by representative open-hearth deoxidation practices. To carry out such studies, it was necessary that a reliable testing procedure for determining the oxygen content of the steel bath and the ingot mold be established. Before entering on any extensive testing program, consideration was given to the available methods of obtaining steel samples and analyzing for oxygen. Testing Procedures It has been shown5-9 that in solidified steel oxygen may ekist in combination with iron, manganese, silicon, aluminum, titanium, chromium and carbon, depending upon the amount of these elements in the sample. In molten steel, however, there has been no direct distinction of the various oxides. Accordingly, the total active oxygen in the molten steel bath is designated by the symbol 0. During deoxidation, various oxides may be present either in solution in the molten steel or as solid or liquid inclusions. Any sample taken from the molten steel for oxygen analysis will include both the dissolved and the mechanically included oxygen. Similarly, samples of the solid steel product will also include the two forms of Oxygen' Methods of Samplirzg the Molten Steel Bath In order to obtain a true oxygen analysis from liquid steel, this element must be completely retained in the solidified sample. Several methods have been proposed whereby this stabilization can be effected. As early as 1915, Kichlinelo proposed a method for testing molten steel, in which the oxygen combined with some added aluminum. The concentration of the resultant aluminum oxide was determined by chemical analysis. This method was

Jan 1, 1945

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By Nicholas J. Grant, John Chipman

A full understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization;the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag—i.e., equilibrium conditions—and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck:20 V radio = % CaO/%SiO, Körber and Oelsen's _ % CaO'. 100/% CaO + % SiO2 where (%CaO') = % CaO- 1.18% P2O5. Herty's B ratio = % CaO - (0.93 . % SO2) - (1.18% P205) Among others there appear the following: 20 References are at the end of the paper.

Jan 1, 1947

By A. C. Losekamp, J. B. Conway

Thermal-expansion data for, tungsten, rhenium, tantalum, .molybdenum, niobium, W-25 pct Re, Ta-10 pct W, ant1 Mo-50 pct Re are presented covering the range from room tempature to 2500°C. In these measureMents, made in a resistively heated tungsten tube furnace operating in a helium atmosphere, data for rod and sheet specimens were found to be identical; in addition, arc-cast and sintered tungsten were found to yield essentially identical results. Optical rneasurenlents of thermal expansion .made in any atmosphere other- than vacuum are subject to a refraction error which can be quite substantial. Specimens tested in helium appear shorter than when tested in racuum and hence a special correction factor must be applied to the helium data in order to obtain accurate results. WHILE it is true that linear thermal-expansion data for many of the refractory metals have been measured to very high temperatures, it is also true that except in a few instances the data from various investigators are not in good agreement. This is particularly evident in the case of tantalum and niobium although some tungsten data have been reported which differ by as much as 40 pct from the data of other investigators. Due to the sensitivity of both tantalum and niobium with respect to impurity absorption during exposure to high temperatures, it is probable that this single factor accounts for the majority of the discrepancies in the thermal-expansion data for these metals. However, this same factor can probably not be employed to explain the existing differences in the tungsten data. In all probability, these are due to errors in the measurement technique, to material composition variations, or to changes which take place in the material during the heating process (e.g., additional densifica-tion resulting from heating a sintered specimen above the original sintering temperature). In view of the discrepancies which exist in the linear expansion data reported for many of the refractory metals, the current study was initiated in an attempt to resolve such differences. Also, no high-temperature linear thermal-expansion data were found to be available for several refractory metals. Providing such data was another objective of the current investigation. MATERIALS In this study test specimens were employed in either rod or sheet form and in several instances both arc-cast and sintered material were employed. Material compositions are presented in Table I. Helium gas was fed to the furnace at a rate of about 0.5 SCFH and no special purification procedures were employed. However, the helium contained less than 50

Jan 1, 1967

By H. S. Kalish, F. J. Dunkerley

Introduction and Previous Work THE determination of the low temperature tensile properties of tin and tin-lead alloys was initiated as part of an extensive research program on the phasial equilibria of tin binary systems below 13.2°C and the property changes associated therewith. A survey of the literature revealed that, although some room temperature tensile data were available for tin and a few tin-lead alloys, there existed no survey report of the low tcmPerature tensile properties of these alloys. Accordingly, the tensile data for tin and a series of pure tin alloys containing from 0.01 to 50 pet lead were measured at eleven temperatures horn — 196 to +20°C and are presented here in survey form. In addition to the importance of these tensile data as a preliminary to certain fundamental research, this information promises also to be of commercial importance because of the extensive use now being made of tin-lead solders in refrigeration and gas liquefaction equipment. Occasional failures of the solders in low temperature service have been attributed by some metallurgists to low temperature embrittlement, while others hold that failure results from the transformation of the tin-rich phase of the solder from the solid white (beta) to the powdered gray (alpha) form. From the data previously available in the literature, neither of these explanations can be completely corroborated. cohen and van Lieshout have estab-lished the beta to alpha tin transformation at 13,2°C and have shown that strain accelerates the transformation. Further, they showed that although I pct lead retarded the transformation, it was not eliminated. It will be pertinent, then, to note whether the beta to alpha transformation of the tin.rich phase will occur in a short-time tensile 'test. polanyi and schmid2 studied the tensile properties of tin single crystals at — 185°~ and report that tin is britlle at this tem-perature. In 1946, Kostenets3 reported that pure tin was brittle at —Ig6 and — 253°~, while lead remained ductile at both these temperatures. He also studied the tensile properties of tin-lead alloys containing from 10 to 75 pet lead at —253, —196 and + I~OC. The ultimate tensile strength increased more than two times in going from room temperature to — I96°C and about three times that value on further cooling to — 253 C- All the alloys were brittle at — 196'C except those containing more than 75 pct lead. Even at — 253'C, the 75 pct lead alloy retained 36 pet elongation in a 30 mm-ga. length. Creep is also an important phenomenon

Jan 1, 1949

By F. D. Rosi, F. C. Perkins, L. L. Seigle

An investigation was made of the mechanism of plastic flow in coarse grained specimens of both sponge and iodide titanium at low (-196°C) and high (500° and 800°C) temperatures. Deformation by slip occurs predominantly on a {1011} plane and in a <1120> direction over this entire temperature range, and secondary slip on {101-1} planes becomes more prevalent with overthisentireincreasing temperature.range, The crystallographic habit of the predominant twin planes becomes more prevalent with type is temperature-dependent, and deformation by twinning increases as the temperature of testing is lowered. Kink bands were not observed at -196OC and rarely at the high temperatures. A LTHOUGH the deform a tional mechanisms in . -titanium at atmospheric temperature have been extensively investigated," there is little information regarding the influence of testing temperature on these mechanisms. The only available data come from the recent work by McHargue and Hammond, who extended single crystals of iodide titanium at a temperature of 815°C. No significant changes in the types of slip and twinning planes were observed, but increased activity on the type I, order 1 pyramidal slip planes and on the type 11, order 2 twinning planes was reported. These planes contribute very little to the deformation process at room temperature.&apos;&apos; &apos; Since there is interest in titanium as a material for use at both low and high temperatures, the present investigation was undertaken to examine the slip and twinning behavior in coarse grained specimens of titanium at -—196", 500°, and 800°C in order to determine the general effect of temperature on the mechanism of plastic deformation. Experimental Material Used and Specimen Preparation—Both sponge and iodide titanium were used in the present investigation; chemical analyses appear in Table I. These materials were arc-melted under argon into 25 g slugs, which were then cold-rolled approximately 90 pct to a sheet thickness of 0.05 in. Since the strain-anneal technique was used for obtaining coarse grains, the cold-rolled sheets were made into tensile specimens which were then annealed to produce a relatively coarse uniform grain structure prior to critical straining. The details of the strain-anneal treatment. size of grains, and the method for preparing the specimen surface for optical microscopy have been described in a previous report.&apos; In order to obtain a wider spread in crystal orientation for the present work, it was necessary to vary the rolling schedule to reduce the degree of preferred orientation in the annealed sheets prior to critical straining. Methods for Tensile Testing—The apparatus for experiments at the temperature of liquid nitrogen (—196°C) consisted of two concentric stainless steel

Jan 1, 1957

By Lester L. Hirst, Arno C. Fieldner, Henry H. Storch

EXPERIMENTAL work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogenation of bituminous coal and tar by the Bergius-.I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 lb. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydrogenation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. EQUIPMENT AND GENERAL PROCEDURE OF RESEARCH The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By R. A. Burmeister, P. E. Greene

Two methods for the synthesis and growth of single crystals of B6 P are described: a solution-growth process employing nickel as the solvent, and a vapor-growth process employing BBr3 and pH3 as the reac-tants. Relevant portions of the Ni-B-P phase diagram have been examined and liquidus data are presented for an isobaric section at an equivalent P2 pressure of 3.8 Torr, and an isothertnal section at 1300°C. Solution-growth techniques are described and the purity and crystalline perfection of the resulting material is discussed. Epitaxial growth of BeP on &P substrates has been obtained using the vapor-phase system. Evidence is presented which supports the assignment of the stoichioknetry B6P to boron sub-plwsphide. THE B-P system differs from other III-V systems in that it contains two distinct compounds. The existence of the monophosphide (BP) has been known for some time,&apos; whereas the subphosphide (B6P) was reported only recently.&apos; Both of these compounds are large bandgap semiconductors (Eg = 2.0 ev for BP~ and 3.3 ev for B6P4), and are therefore of interest for optoelectronic applications. The crystal structure of B6P is quite different from those of most semiconductors, being derived from that of a-rhombohedral boron by the incorporation of the two phosphorus atoms in the intericosahedral sites of the a-boron unit cell?76 B6P also exhibits a number of unusual characteristics, including a high degree of chemical inertness, hardness, and high-temperature stability. No information concerning other physical properties is available in the literature. The present study is part of a broader investigation of the preparation and properties of B6P. This paper considers methods of growing single crystals of B6P of suitable size and quality for physical-property measurements. A detailed discussion of the electrical and optical properties of B6P will be given elsewhere.&apos; GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP&apos; according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .&apos;" It is therefore possible, in principle, to apply several of the reactions reported for the synthesis of BP to the synthesis of B6P merely by selecting lower phosphorus pressures or higher temperatures, in accordance with the equilibrium data. Other techniques for the direct synthesis of microcry stalline B8P have also been reported.1°

Jan 1, 1968

By D. C. Hilty, W. Crafts

Determination of the solubility of oxygen in iron containing silicon, or manganese, or both, has confirmed the earlier work on silicon, shown that manganese is more effective than expected, and has demonstrated that the combination of silicon and manganese is a much stronger deoxidizer than might have been inferred from their individual effects. SILICON and manganese are of primary impor-tance in the deoxidation of steel, and a study has been made at the Union Carbide and Carbon Research Laboratories, Inc. of the solubility of oxygen in iron in the presence of silicon and manganese, singly and in combination, as a basis for more effective control of inclusion formation. The investigation was carried out with the same equipment and experimental procedure that were used in the determination of the oxygen solubility of iron containing aluminum&apos;. The heats were melted in a rotating crucible furnace under an argon atmosphere. Bath temperatures were controlled by platinum/platinum +10 pct rhodium thermocouples to attain equilibrium at 1550°, 1600°, and 1650°C, so that oxygen solubility isotherms were determined directly without requiring calculation from a temperature coefficient. A detailed description of the furnace and procedure is given in the paper on aluminum deoxidation1. Oxygen solubility in the presence of more than 0.10 pct silicon was found to approximate earlier determinations closely, but some deviation was observed at lower silicon contents. Manganese appeared to be more effective than had been anticipated. The combination of silicon and manganese lowered the solubility for oxygen markedy as compared with either silicon or manganese alone. Although the solubility for oxygen in the presence of both silicon and manganese represents only a part of the information needed to control inclusion formation, it suggests a partial explanation of the benefits of this combination that have been observed in practice. Manganese and Oxygen in Liquid Iron: The study of oxygen in iron in the presence of manganese was carried out in magnesia crucibles of the type furnished commercially for laboratory induction furnaces. Alumina crucibles were unsatisfactory, because the work on the aluminum-oxygen equilibria in iron&apos; had shown that merely melting iron in an alumina crucible limited the solubility of oxygen to a level considerably below that anticipated for moderate concentrations of manganese. Silica crucibles appeared unsuitable because of the dangers of excessive fluxing by the melt. Moreover, as will be shown later, melting iron in a silica crucible also limits the oxygen content below that in equilibrium with

Jan 1, 1951

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1&apos;2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O&apos;s. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO&apos;s are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.&apos; At 900°C noticeable decomposition takes

Jan 1, 1964

By M. Cohen, B. L. Averbach

Many hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or sub-atmospheric coo1ing.l,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained . steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1949