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By Robert I. Jaffee, Bruce W. Gonser

Recent work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. Materials and Alloying -4s in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni. and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about I050 C, and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. Thermal Analysis In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,' a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By A. H. Willis

In this paper the results of an exploratory study conducted by personnel of the Knolls Atomic Power Laboratory on 18.6, 22, and 40 wt pct uranium-zirconium alloy will be presented. LARGE power output and long life or endurance from small, compact nuclear reactors require the use of enriched uranium for a fuel material. However, the ability to remove heat from the element, the tolerable fission product concentration, or some physical limitation of the system can limit the allowable fuel enrichment, or the volume of the fuel. In such an event, the fuel-element designer must find a suitable diluent for the uranium. Zirconium is an attractive material for such a purpose as it has good nuclear properties and a low absorption cross section. Because it has a good corrosion resistance in water, zirconium is a suitable cladding and the uranium-zirconium alloy makes a good core material. The alloy has a high thermal conductivity, a low elastic modulus, and a low thermal-expansion coefficient, all of which tend to minimize the thermal stresses in the core. Furthermore, the unirradiated material is reasonably ductile and has adequate strength. DESCRIPTION OF SAMPLES Two types of cylindrical samples were used in this study 1) short, 1/2-to 1-in.-long samples to test the irradiation stability of the alloy and 2) 2-ft-long samples to investigate the resistance of an element to longitudinal deformation. Composite samples having 0.060-to 0.140-in. core diameters and clad with a 0.010-in. thick zirconium jacket were fabricated by coextrusion and by hydrostatic pressure bonding of the cladding to the preformed core material. Both fabrication processes produced the uniform metallurgical core-to-cladding bond which was felt necessary to minimize the uncertainty of the central core temperature. Both consumable-arc and induction-melting techniques were used to melt the uranium-sponge zirconium core alloy. Since a graphite crucible was used in induction-melting this alloy contained more carbon impurity, which resulted in a finer grain size than the arc-melted alloy. The core to cladding interface was uniform in elements coextruded from the fine-grain, induction-melted core material, while those elements fabricated using arc-melted core material had very irregular interfaces because of the coarser grain size. Both cold-worked and heat-treated fuel materials were irradiation tested. Cold-worked alloys were swaged to about a 5 pct final reduction in area without subsequent annealing. The heat-treated alloys were heated to 800°C, held at temperature for 15 min and furnace-cooled to about room temperature. This

Jan 1, 1960

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By Robert I. Jaffee, Bruce W. Gonser

RECENT work by the authors1 established the constitutional diagram of the gold-germanium system. Of particular interest in the simple euctectiferous system was the eutectic alloy at 12 per cent Ge, which melted at the very low temperature of 356°C. and had an unusually fine eutectic structure. It was of interest to investigate the effect of third components on the melting point, microstructure, and strength of this alloy, and in this work the effect of copper is discussed rather completely, with less complete data on the effects of silver, platinum, nickel, and zinc. No reference in the literature has been found on ternary systems with gold-germanium. MATERIALS AND ALLOYING As in the work on the binary system, gold-germanium, the germanium used in this investigation was the cyanide-reduced, 99.9 per cent product, produced by the Eagle-Picher Co. Fine gold sheet from Handy and Harmon, pure platinum sheet from the American Platinum Works, copper magnet wire from Anaconda, nickel wire assaying 99.6 per cent Ni, and electrolytic zinc were used for alloying. To make the alloys, charges of the pure metals were put in a graphite crucible and melted in an atmosphere of pure hydrogen. The temperature was brought up to about 1050°C., and the metal allowed to freeze in the crucible. Except with alloys containing zinc, melting losses were consistently less than a few milligrams. When zinc was a component, weight losses up to half the weight of the zinc present were incurred, and the alloy compositions were calculated by assuming the entire weight loss to be that of zinc. In all other cases the composition of the alloys could safely be taken as that of the charge. The ingots, as solidified, were segregated, the heavier primary phases being at the bottom and sides of the ingots and the lighter primary phases at the top, but by sectioning the entire ingot vertically for microscopic examination, this factor could be evaluated. Ingots for microscopic examination weighed one gram, and those for thermal analysis weighed three grams. THERMAL ANALYSIS In this work, the eutectic line composition and thermal arrests were desired, and, after microscopic exploration had established the position of the eutectic line at a given percentage of the third component, a thermal analysis was run at that composition. The method of thermal analysis used in the work on the binary Au-Ge system,1 a method particularly well suited for a small quantity of material, was used in this work. Clearly defined arrests were obtained, although with some alloys containing platinum

Jan 1, 1946

By R. S. Dean

THE commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in MINING AND METALLURGY for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for "the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. PRACTICE AT BOULDER CITY The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: I. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By D. J. McAdam

In a recent survey of the literature, the author has found evidence incompatible with prevalent views regarding the technical cohesive strength and yield strength of metals. Some of the evidence regarding the technical cohesive strength was presented in a previous paper,21 and views were presented that are believed to be in better accord with the evidence. In that paper, it was shown that the technical cohesion limit (contrary to prevalent views) varies with the combination of principal stresses,t and that the influence of plastic deformation on the technical cohesive strength is not in accordance with prevalent views. In this paper, consideration will be given to both the technical cohesion limit and the yield stress as affected by the combination of principal stresses. Evidence will be presented that the variations of the yield stress and the technical cohesion limit with the combination of principal stresses are not in accordance with prevalent views. Consideration will also be given to ductility and work-hardening capacity, which depend on the initial difference between the technical cohesion limit and the yield stress. By the "technical cohesion limit" is meant the mean stress at actual or poten- tial* fracture. An example of a rechnlcal cohesion limit is the "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. The cohesion limit thus obtained for a ductile metal, however, has been greatly altered by the plastic deformation. It is important to consider the cohesion limit of the metal prior to this deformation, and the variation of the cohesive strength with plastic deformation. The relation between the cohesion limit and the corresponding flow stresst determines the ductility of a metal and the energy that it will absorb before fracture. In this paper, as in the previous paper,21 tensile stresses will be viewed as positive and compressive stresses as negative. The algebraically greatest principal stress will be designated S1, the least principal stress will be designated S3, and the intermediate principal stress will be designated Sz In the previous paper, attention was confined to stress combinations with two of the principal stresses equal (with the intermediate principal stress S2 equal eithel to S3 or 31). In this paper, consideration will also be given to the effect of stress combinations with all three principal stresses unequal. In the earlier sections of the paper (pp. 3I I to 324), attention will be confined to stress combinations with

Jan 1, 1942

By D. J. McAdam

In a recent survey of the literature, the author has found evidence incompatible with prevalent views regarding the technical cohesive strength and yield strength of metals. Some of the evidence regarding the technical cohesive strength was presented in a previous paper,21 and views were presented that are believed to be in better accord with the evidence. In that paper, it was shown that the technical cohesion limit (contrary to prevalent views) varies with the combination of principal stresses,t and that the influence of plastic deformation on the technical cohesive strength is not in accordance with prevalent views. In this paper, consideration will be given to both the technical cohesion limit and the yield stress as affected by the combination of principal stresses. Evidence will be presented that the variations of the yield stress and the technical cohesion limit with the combination of principal stresses are not in accordance with prevalent views. Consideration will also be given to ductility and work-hardening capacity, which depend on the initial difference between the technical cohesion limit and the yield stress. By the "technical cohesion limit" is meant the mean stress at actual or poten- tial* fracture. An example of a rechnlcal cohesion limit is the "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. The cohesion limit thus obtained for a ductile metal, however, has been greatly altered by the plastic deformation. It is important to consider the cohesion limit of the metal prior to this deformation, and the variation of the cohesive strength with plastic deformation. The relation between the cohesion limit and the corresponding flow stresst determines the ductility of a metal and the energy that it will absorb before fracture. In this paper, as in the previous paper,21 tensile stresses will be viewed as positive and compressive stresses as negative. The algebraically greatest principal stress will be designated S1, the least principal stress will be designated S3, and the intermediate principal stress will be designated Sz In the previous paper, attention was confined to stress combinations with two of the principal stresses equal (with the intermediate principal stress S2 equal eithel to S3 or 31). In this paper, consideration will also be given to the effect of stress combinations with all three principal stresses unequal. In the earlier sections of the paper (pp. 3I I to 324), attention will be confined to stress combinations with

Jan 1, 1942

By F. R. Hensel

PURE silver and silver-lead alloys have been studied as to their suitability for bearings.1-8 A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materials.† The silver-rich end of the diagram as reported in the literature9-11 was found to be sketchy and it was necessary to carry out considerable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. TEST MATERIALS In the beginning of the work, only fused alloys were investigated. Later, research [TABLE I. Composition of Fused Silver thallium Alloys Tested for Antifriction Properties PERCENTAGE ALLOY No.OF THALLIUM 15330.48 153406 231 HT2.04 2312.10 232 HT3.83Balance 2324.07Silver 233 HT5.86 2336.38 2349.84 234 HT10.07] was carried out on electroplating methods and diffusion processes. In preparing the fused alloys, care was taken to exhaust the toxic fumes caused by the thallium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in. diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr2O7, 8 c.c. H2SO4, and 100 c.c. H2O. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C. show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475°C. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not result in complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1945

By Laurence Delisle, Aaron Finger

THE alloys formed by the addition of nickel to iron by convelltional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.? owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect could be obtained in alloys of iron and nickel prepared by powder metallurgy technique. PROCEDURE Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, 0.001 5 ; lead, 0.035; tin, 0.025 ; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A representative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 3 2 5-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the surfaces of the particles. The reduced powders, slightly caked, were ground in a mortar and screened again through a 325- mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hydraulic presses. The pellets were compacted in a cylindrical die, ½ in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specifed for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By D. J. McAdam, R. W. Mebs

The technical cohesive strength of a metal means, not the interatomic forces, but the technically estimated resistance to fracture. An example of such resistance to fracture is the so-called "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. According to the prevalent view,8 the technical cohesive strength of a metal. in any particular state as regards prior mecharlical treatment and heat-treatment, is determined by a limiting value of the algebraically greatest principal stress. In two previous papers by one of the authors, evidence was presented to indicate that the technical cohesive strength of a metal cannot be represented by a single stress value, but that it comprises an infinite number of values corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength thus comprises an infinite number of technical cohesion Limits, each representing a specific stress combination at fracture. In the same papers, evidence was presented that plastic extension causes a continuous increase in the technical cohesive strength. Such a variation is not in accordance with the prevalent view that plastic extension first increases, then decreases, the technical cohesive strength.' In this paper, as in the previous papers,14.15 the algebraically greatest principal stress will be designated S1, the least principal stress will be designated 33, and the intermediate principal stress will be designated S². The technical cohesion limit under polarsymmetric tension (S1 = S2 = S3) will be termed the "disruptive stress," and the cohesion limit under unidirectional tension (S2 and S3 = o) will be termed the "severing stress."l4, .l5 The yield strength of a metal, according to the generally accepted theory, may be represented by a constant value of the shearing-strain energy, and hence by a constant value of the sum of the squares of the three principal stress differences. In the second of the previous papers,15 however, evidence was presented that the limiting yield stress decreases with increase in the volume stress, the algebraic average Of the three principal stresses.* This in fluence of the volume stress becomes prominent only in the field of triaxial tension. In the two previous papers,".'5 diagrams were presented to show the variation of the technical cohesion limit, yield stress, and ultimate stress with the combination of principal stresses and with plastic extension. Those diagrams and the resultant • Any stress system ma? be resolved into a polarsymmetric stress causing pure volume strain and a combination of pure shearing stresses. which cause no change of volum

Jan 1, 1945

By Carl A. Zapffe, George A. Moore

IN a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal sub- structures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the "disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, un- affected by chemical attack and undistorted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. MATERIALS STUDIED In commercial steels, defects caused by hydrogen take various external forms ac- cording to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement-"pickling brittleness"-in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free- machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This , choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group I: Prepared from Armco Ingot Iron As shown in Table I, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By Laurence Delisle, Arron Finger

The alloys formed by the addition of nickel to iron by conventional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.$ owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect coulcl be obtained in alloys of iron and nickel prepared by powder metallurgy technique. Procedure Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating Co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, o.oo15; lead, 0.035; tin> 0.025; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A repre-sentative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 325-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the sur-faces of the particles. The reduced pow-ders, slightly caked, were ground in a mortar and screened again through a 325-mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hy-draulic presses. The pellets were com-pacted in a cylindrical die, 34-in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specified for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By Arron Finger, Laurence Delisle

The alloys formed by the addition of nickel to iron by conventional metallurgical procedures show physical properties that differ widely from those of the individual metals. The effect of alloying on the mechanical properties is most pronounced in alloys containing between 15 and 25 per cent nickel. The tensile strength of an alloy containing, for example, 20 per cent nickel and 80 per cent iron (with 0.06 per cent carbon), in an annealed condition, is above 150,000 lb. per sq. in.$ owing to a martensitic type of transformation, as compared with about 50,000 lb. per sq. in. for pure iron in the same condition. The object of this work was to determine whether the same beneficial alloying effect coulcl be obtained in alloys of iron and nickel prepared by powder metallurgy technique. Procedure Bars and pellets for tension and compression tests, respectively, were made. Two groups of specimens were prepared: (I) by cold-pressing the powders and sintering; (2) by cold-pressing the powders, sintering, repressing and resintering. Raw Materials Nickel powder supplied by Metals Disintegrating Co., marked MD-151, was used. A typical analysis of this powder was as follows: sulphur, 0.040 per cent; copper, 0.18; iron, 0.23; manganese, 0.002; magnesium, o.oo15; lead, 0.035; tin> 0.025; silicon, 0.08; chromium, 0.008. Electrolytic iron powder supplied by Plastic Metals Inc. was used. A repre-sentative chemical analysis for impurities other than gases, supplied by the vendor, gave the following results: carbon, 0.005 per cent; manganese, 0.002; silicon, 0.003; phosphorus, 0.001; sulphur, 0.004; nickel, 0.008. The fractions from these powders passing a 325-mesh sieve were reduced in hydrogen at 600°C. for one hour, to clean the sur-faces of the particles. The reduced pow-ders, slightly caked, were ground in a mortar and screened again through a 325-mesh sieve. Mixing The proper proportions of the powders were mixed overnight on rolls, in glass jars fitted with iron-wire baffles to break aggregates of particles that might form. Pressing All specimens were compacted on hy-draulic presses. The pellets were com-pacted in a cylindrical die, 34-in. diameter. The ratio of thickness to the diameter of the pellets was maintained as nearly as possible at 0.9, as specified for standard short compression pieces. The tensile bars were made by compacting 30 grams of powder. Their shape is shown in Fig. I. The compacting pressures for the pellets and the tensile bars were:

Jan 1, 1946

By Carl A Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By Carl A. Zapffe, George A. Moore

In a previous publication from this laboratory1 the conclusion was drawn that the embrittling effect of occluded hydrogen on iron and steel must result from the precipitation of the gas within small openings through the crystal structure. A review of the literature then published indicated the real existence of crystal substructures of the mosaic type and gave presumptive evidence that the "rift openings" associated with hydrogen occlusion are the same as the L'disjunctions" of the mosaic theory. Inasmuch as no clear conception of the actual nature of the crystal fragments and openings inherent in these theories has been established, it was considered desirable to obtain direct micrographic evidence of their true configuration. In this direction the standard methods of metallographic attack have proved useless. Recourse was had, therefore, to the direct examination of the surfaces upon which failure by cleavage had resulted from the presence of hydrogen. It was expected that such a surface, unaffected by chemical attack and undis-torted by polishing, would reveal the fine openings penetrated by the gas and thus indicate the real nature of the substructures. Materials Studied In commercial steels, defects caused by hydrogen take various external forms according to such factors as structure and purity, and to the extent to which hydrogen either occludes or produces chemical changes. The present work relates only to the well-known transcrystalline hydrogen embrittlement—-"pickling brittleness "—in which elemental hydrogen occluded within the grain develops cleavage characteristics. For example, hydrogen embrittlement resulting from hydrogen reaction products is excluded from detailed study. It was also desirable, as far as possible, to have the study uncomplicated by other elements which themselves cause brittleness. Three types of iron were used. These included ingot iron, decarburized free-machining steel, and a specially prepared, aluminum-killed, electrolytic iron. This choice allowed a comprehensive selection of unavoidable minor impurities and inclusions, which could subsequently be shown to have no specific effects on the structures within the grains. Carbon, and any other impurities free to react with hydrogen, were first removed by a preliminary annealing treatment in hydrogen. Subsequent treatment in vacuo extracted much of this hydrogen and its gaseous reaction products. The resultant ductile iron was then embrittled either by a second anneal in hydrogen, followed by rapid cooling, or by cathodic electrolysis. Group 1: Prepared from Armco Ingot Iron As shown in Table 1, the principal impurity in this iron was oxygen, which survived the purifying treatment to a large extent. Two series were prepared. The first (Nos. SIO-24) was purified only one day in hydrogen and dehydrogenized one day in nitrogen. Containing both hydrogen and its

Jan 1, 1943

By H. B. Pulsifer

One of the most common basic open-hearth furnace products is a simple carbon steel with a carbon range from 0.05 to 0.15 per cent. The material is widely used for sheets, tubes, bars, wire and the innumerable special objects of secondary fabrication. The properties of the material vary over wide ranges, depending on the more exact composition and details of manufacture or treatment that affect its structure. The present paper is a review of those properties and structures that have been found by studying this steel as used in the cap screw industry. At first glance this might be thought a narrow application of the steel, but, since the industry uses the material in the cold-worked, annealed and heat-treated conditions, the title of the paper may be excused for its comprehensiveness. Yet, in studying the wide ranges of properties and structures that preclude a more specific title, there can be no suggestion of completeness or finality. Even a summary of a few years' work is no more than a preliminary survey of a field that will be fertile in scientific data and industrial products for many years to come. An outline of the structures will be given first, then a list of the previous contributions that are at hand and finally some details of the work and related problems, especially concerning this low-carbon steel in the surface-hardened condition. Wire Used in Manufacture of Cap Screws The wire that is used for making cold-upset and roll-threaded cap screws has been cold-drawn from hot-rolled rods that were pickled and limed. The common sizes used in the industry range from 0.185 to 0.750 in. dia., the exact diameters depending on the plant practice and having the usual tolerances of 0.002 in. for the smaller sizes and 0.003 in. for the larger sizes. The carbon range, by pit analysis, is usually between 0.07 and 0.12 per cent. Manganese should be within the usual 0.30 to 0.50 per cent. range. Sulfur rarely exceeds 0.045 per cent. and phosphorus seldom exceeds 0.030 per cent. Silicon is usually below 0.03 per cent. but in the silicon-killed steels may be in the customary 0.10 to 0.25 per cent. range. Rimmed steel is not considered most suitable for cap screws that are cold-headed or for parts that are to be surface-hardened.

Jan 1, 1931

By F. H. Wilson, E. W. Palmer

Brass mills are familiar with a recurring problem which reveals itself during deformation of annealed metal as an opening up of cracks which are suggestive of a grain boundary pattern. A typical example is seen in Fig 1, which shows part of the convex surface of a cartridge brass disc which was slightly dished by the punching operation. Another illustration of the same type of defect was found in the surface of a finished cartridge case which split open on firing. These cracks, shown in Fig 2, were away from the split but indicate the presence of the type of weakness which permitted the splitting. Usually the weakness consists of separate cracks, the lengths of which are of the same order of magnitude as the grain size prior to the final anneal. Their typical appearance in a polished section is shown in Fig 3. This structure was found below the surface of a fractured tensile-specimen that had been cut from a large cartridge blank showing the defects on its convex surface. While the pattern formed by these cracks suggests a grain boundary origin, the cracks bear no relation to the currently existing grain structure. Thus Fig 3 shows that the grains have grown up to cracks already present. Since it is doubtful that the cracks were present in the metal before the anneal, they must have formed during the anneal but prior to recrystallization. The term "fire-cracking" has been generally applied to cracking that occurs during an anneal under the influence of internal stress, but refers more specifically to obvious macroscopic cracking attributable to the presence of a low melting phase, usually lead. Since the type of cracking described above may occur when the lead content is very low, we have considered it a somewhat different phenomenon, and have called it "inter-granular parting." While most examples involve cartridge brass, intergranular parting has also been observed in the fabrication of large seamless tubes from discs of both 85/15 red brass and 70/30 cupro-nickel. Similar cracking in nickel silver was investigated by Jones and Whitehead,1 who showed that it could occur during healing or cooling. That which occurred on heating they called "fire cracking," and they suggested that, a transformation at about 320°C might account for its occurrence. It was felt in this laboratory that the observed parting was probably one aspect of the general observation, first made by Rosenhain and Archbutt,2 that a tendency toward intergranular fracture under tensile stress increases with increasing temperature and decreasing rate of strain. In this case the stress involved would be internal. The rate of strain would be exceedingly slow, a localized internal creep. Reference to the literature uncovered no efforts to extend the observations of Rosenhain to conditions involving only internal stress. Accordingly, an exploratory research, sufficient in detail to satisfy us as to the probable truth of this explanation of the observed intergranular parting, was undertaken. The internal stresses present during the early stages of an anneal (prior to recrystallization) would be from two sources: residual stresses developed during deformation, and thermal stresses caused by uneven heating and expansion. Thermal stresses would vary widely according to shape, size and manner of heating, and can be considered as supplementary to residual stresses. It seemed necessary to determine the stress and temperature conditions under which parting would occur in a relatively short time, and then to establish whether or not in- ternal stresses may persist to an extent adequate to cause parting at such temperatures. (Jones and Whitehead1 and Moore and Beckinsale3 made tests which indicated that stress relief required an appreciable time.) During the course of the research the desirability of studying the effect of grain size became apparent, and this factor is one of the major variables of our investigation. Intergranular Parting under Tension at Elevated Temperatures In early experiments, hard 70/30 brass tensile specimens, with unknown residual stresses, held for 10 min. at applied stresses from 30,000 to 40,000 psi at temperatures from 300 to 350°C, showed no macroscopically visible cracks when unloaded and cooled, but cracks very similar in appearance to those observed in commercial practice were revealed in these specimens by pulling them to fracture. Annealed specimens, on the other hand, showed no cracks in such experiments, apparently because they deformed plastically at stresses below those necessary to cause parting in a reasonable time. Hence, the specimens used for this study were first strengthened by cold tensile elongation, giving them an unavoidable residual stress pattern (determined largely by grain size and orientation) which would, however, correspond in direction, at least, to the stress pattern obtained under stress at temperature. A variation in these residual stresses might be expected with variations in grain size, but following any given anneal the reproducibility of stress pattern should be as good as that of the grain size measurement. With no information as to the effect of the amount of prior deformation, tests were conducted on specimens given the same cold elongation, using a stress applied at temperature which was a constant proportion of the stress required to produce this elongation. In

Jan 1, 1950

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron' and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970

By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970