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By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

This paper deals with the results obtained and the techniques employed in determining: 1. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battellc Memorial Institute. Liquidus and Solidus Temperatures of HH and HT Type Alloys Experimenta1 Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency, induction furnace and poured into a core-sand mold for cooling. The temperature measurements were obtained by means of a platinum, platinum-rhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and North-rup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600' to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures "re shown on Fig. I for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By Harold Markus, Gerhard Derge, Arthur Grobe

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from ½ to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.1°. Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

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 C. R. Taylor, John Chipman

THE study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8: I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. EXPERIMENTAL METHOD Furnace The furnace used in this investigation differed from previous designs and may be considered a fourth modification of the original rotating furnace. Its essential features are shown in Fig. I. The outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base C are alberene stone. The coil supports D are of "Formica," a material formed from phe-

Jan 1, 1942

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 C.R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I' The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By C. R. Taylor, John Chipman

The study of chemical reactions of liquid steel and basic open-hearth slag involves a complex slag system of at least eight important components, and often a number of others. In initiating an experimental program on the equilibrium relationship of slag and metal, it became evident that but little progress could be expected in the interpretation of the complex slags until an understanding had been gained of the simpler liquid systems composed of a limited number of slag constituents. The simplest system that in any way resembles open-hearth slag must contain lime, silica and iron oxide. Attempts to produce in an induction furnace slags containing only these constituents have met with serious limitations because of the solubility of refractories in the slag. Thus in acid-lined furnaces the slag is always saturated with silica and consequently contains between 48 and 63 per cent of this component. In basic-lined furnaces an undesired additional component, magnesia, is introduced to the extent of some 3 to 15 per cent, depending upon the acidity, sometimes with disastrous results to the furnace. Thus in a magnesia-lined furnace, Fetters and Chipman1 found it impossible to prepare slags in which the ratio (CaO + MgO)/SiO2 was less than that corresponding to the metasilicate (approximately 0.8:I). Between this composition and that of the true acid slags lies a field of composition about which very little is known and which cannot be explored by any ordinary means. This circumstance, as well as the desire to study the more basic slags in the absence of magnesia, calls for the development of a method by which slags may be brought into equilibrium with molten metal without coming in contact with refractory. Such a technic has been provided by the rotating induction furnace developed by Barrett, Holbrook and Wood.2 Three modifications of the rotating furnace were described by these authors. The first was essentially a rotating refractory cylinder containing the magnesia crucible, which was itself heated by a graphite crucible. In the second, only the magnesia crucible rotated, the cylindrical graphite heater being stationary. In the third, the coil and crucible revolved, and the metal was heated directly by induction. Experimental Method Furnace The furnace used in this investigation differed from previous designs and may be Sci- a fourth modification of the original rotating furnace. Its essential fea tures are shown in Fig. I' The Outer case A is a fire-clay flue liner for control of the atmosphere. The top B and base 6 are alberene stone. The coil supports D are of ""Formica," a material formed from phe-

Jan 1, 1943

By Gerhard Derge, Arthur H. Grobe, Harold Markus

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By Harold Markus, Arthur H. Grobe, Gerhard Derge

The high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as tcrne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys. 1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. Apparatus and Method The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from M to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.† After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been clamped. The pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. + 0.1". Potentials were measured against a saturated calomel electrode connected to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By A. C. Fieldner, Lester L. Hirst, 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 hydrogehation 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 Ib. 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-hydro-genation 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 Lester L. Hirst, Henry H. Storch, A. C. Fieldner

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 hydrogehation 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 Ib. 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-hydro-genation 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. 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 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,' whereas the subphosphide (B6P) was reported only recently.' 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.' GENERAL CONSIDERATIONS The method first used to synthesize B6P was the disproportionation of BP' according to the reaction The equilibrium P2 pressures corresponding to this reaction were also determined .'" 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 H. Cecil Spicer

The results described in this article are based on field work conducted during the periods APril-May, 1939, and MaY-JulY, 1940. The United States Potash CO. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation mas completed under a cooperative arrangemerit made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an l was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedell and Messrs. Schlumberger2 reported geophysical work performed in the disrovery of the salt domes of Alsace; Carrette and Kelly3 described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlum-berger5 in a communication. Messrs. Alty6 described studies 0" salt deposits in which the sing[e-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performetl with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 800 ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,ll through the courtesy of Harry Aurand, of the Midwest Refining CO.

Jan 1, 1942

By J. Russ, C. L. Clark

For many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. Influence of Rate of Deformation on High-temperature Properties It is not the intent of this paper to survey all the work that has been done On the effect of deformation rate On the properties of metals. The importance of this factor, however, was shown by Zay Jeffries' as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature' Fig. I is a diagrammatic sketch showing the effect of temperature On the relative strength of the crystals and grain boundaries and the type of fracture that will res depnding On the location of the test, or Or temperature with respect to the equicOhesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains: while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent On the deformation rate' For example, in 0.15 per cent plain carbon steel the location of this temperature under

Jan 1, 1947

By C. L. Clark, J. Russ

For many years attempts have been made to develop a laboratory test that would serve to indicate the proper temperatures to be used in the various hot-working applications to which metals may be subjected as they are being processed from the cast ingot to the desired finished products. That these attempts have not been very successful is indicated by the fact that most of the temperatures in use today in these operations have been developed over a period of years by trial and error. In other words, the selection of the proper temperatures for the hot-working of metals is generally an art rather than a science. Our knowledge with respect to the behavior of metals at elevated temperatures has been greatly extended during the past several years. While most of the work in this field has been done at proposed operating temperatures of equipment, rather than at processing or fabricating temperatures, one outstanding fact has been developed, which is applicable to the entire high-temperature range; that is, that the rate of deformation to which the metal is subjected is of the same order of importance as the temperature. The failure to properly recognize this fact has greatly retarded the development of a suitable laboratory test for determining hot-working temperatures. Influence of Rate of Deformation on High-temperature Properties It is not the intent of this paper to survey all the work that has been done On the effect of deformation rate On the properties of metals. The importance of this factor, however, was shown by Zay Jeffries' as early as 1919, when he called attention to the existence of the so-called equicohesive temperature and to the effect of certain factors on the location of this temperature' Fig. I is a diagrammatic sketch showing the effect of temperature On the relative strength of the crystals and grain boundaries and the type of fracture that will res depnding On the location of the test, or Or temperature with respect to the equicOhesive temperature. Since the type fracture varies, it also follows that at temperatures below the equicohesive temperature the major deformation occurs in the grains: while at temperatures above, the deformation results either from the movement of the grains with respect to each other or recrystallization of the strained material occurs almost instantaneously, producing new crystals at the fracture. As previously indicated, it is an established fact that the position of this equicohesive temperature for any given metal is dependent On the deformation rate' For example, in 0.15 per cent plain carbon steel the location of this temperature under

Jan 1, 1947

By H. Cecil Spicer

The results described in this article are based on field work conducted during the periods APril-May, 1939, and MaY-JulY, 1940. The United States Potash CO. is mining potash on Government land under a permit from the Department of the Interior and the geophysical investigation mas completed under a cooperative arrangemerit made between that company and the Conservation Branch of the Geological Survey. The writer, a member of the Section of Chemistry and Physics of the Geologic Branch, was assigned to this investigation. Four definite objectives were in mind for the geophysical work in the studies over the salt deposits. The first was to determine the measure of success that could be attained in this type of work with the resistivity methods that were to be employed. These methods had been introduced into the work of the Conservation Branch by Benjamin E. Jones for the investigation of dam sites, and have been used under his direction by the author for such work. If the method proved to be applicable, an l was to be made to contour the top of the salt beds and also the other formation boundaries known to be present in this area. Salt-water aquifers were to be studied in an effort to determine their boundaries, and an attempt was to be made to delineate the potash-bearing beds. Others have made, and reported, resistivity studies over saliferous deposits in different areas. Friedell and Messrs. Schlumberger2 reported geophysical work performed in the disrovery of the salt domes of Alsace; Carrette and Kelly3 described the geology of the same area. Leonardon and Kelly4 published a resistivity curve obtained over the Hettenschlag dome, and a further discussion of this same area was given by the Messrs. Schlum-berger5 in a communication. Messrs. Alty6 described studies 0" salt deposits in which the sing[e-probe method was used. Sinerez7 mentions that electrical methods were tried over salt deposits in Spain. Geoffrey and Charrin8 show a resistivity curve obtained over marl, gypsiferous marl and salt which is similar to that obtained over the New Mexico salt deposits. Kelly9 reported resistivity work performetl with the ground comparator of Zuschlag over the salt deposits near Syracuse, N. Y., where the Salina formation is at a depth of 700 to 800 ft. Some structural studies on the potash basin of Alsace are described by Poldini.10 Another single-probe resistivity study, made over salt deposits in New Mexico, is briefly described by Heiland,ll through the courtesy of Harry Aurand, of the Midwest Refining CO.

Jan 1, 1942

By J. T. Michalak, H. W. Paxton

The recovery of the initial flow stress of poly-crystalline iron is characterized by a) a logarithmic time dependence; b) an increasing activation energy with increasing recovery; c) an increased ?,ate and fraction of recovery with decreased temperature of deformation; and d) an increased rate with increased deformation. Isochro)ml studies of the recovery of single crystals revealed more sluggish recovery. The original flou3 stress of single crystals could be regained by recovery anneals at 800"or 900°C. ThE great majority of the theoretical treatments and experimental studies of strain-hardening have been concerned with the close-packed lattices.' Very little effort has been expended on the bcc structure so that the theory of work-hardening of this lattice is essentially nonexistent. The limited amount of experimental data resulting from the direct studies on silicon-iron,2 low-carbon steel,3 and purified irons4"7 does not as yet permit a detailed analysis of the strain-hardening. Studies concerned with the effects of annealing following deformation have been few in number," have been somewhat limited in extent, and have had the disadvantage of using irons containing a substantial impurity content. The present research was undertaken to augment the limited knowledge we have of the characteristics of a bcc metal as regards strain-hardening and recovery from the strain-hardened state. The recovery of the flow stress has been employed since it was felt that the stress associated with the hardened state gives at least a fair qualitative description of the state of the imperfections causing the hardening. The study was concerned primarily with the recovery of flow stress following strain-hardening of polycrys-talline, zone-melted iron as a function of the amount of deformation, the temperature of deformation, and the time and temperature of the recovery anneal. A limited investigation of the recovery of the initial flow stress of single crystals of this same material as a function of the recovery temperature was also conducted in conjunction with the Lambot X-ray technique." MATERIAL The zone-melted iron used in this investigation was obtained through the courtesy of the American Iron and Steel Institute and Battelle Memorial Institute. The analysis, as given by the supplier indicated a maximum impurity content of 0.02 wt pct excluding those impurities listed in Table I. (The actual impurity content is very probably less than this since detection limits were considered as the amount of a particular impurity level.) Also listed in Table I are the interstitial impurity contents of the iron at various stages of experimental work indicating that these im-

Jan 1, 1962

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

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