Search Documents

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By Paul A. Beck, John Towers, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By John Towers, Paul A. Beck, W. D. Manly

Recent work on grain growth in high purity aluminum and in a solid solution type alloy of aluminum and magnesium1 showed that the isothermal increase of the average grain diameter D with time follows the equation D = K(tg + A)2 Eq 1 Here tg is that portion of the total annealing time 1, which is available for grain growth, that is the annealing time less the time necessary for complete recrystallization. The parameters A and n depend only on the temperature. A has the dimension of time, and is usually of the same order of magnitude as the time for recrystallization: R. In some instances R may be substituted for A in Eq I. This is the case for example at long periods of annealing or at high temperatures, where both A and R become small in comparison with t. In such instances Eq I is simplified to D = K, tn Eq 2 For high purity aluminum the exponent n increases in the ratio of about I to 5 in. the temperature range of 350' to 6w°C. 70-30 brass has been long known to exhibit grain growth of the continuous type, such as occurs in pure metals. For this reason, it was of interest to determine whether grain growth in brass also follows Eq I and 2 as it does in aluminum. Isotherma1 grain growth data for 70-30 brass were published in recent years by R. S. French2 and by H. L. Walker.' Fig I shows a log D vs. log t plot of French's data, together with the 500, 600 and 700°C data by Walker for 42.8 pct reduction by rolling. In such a log D vs. log t plot Eq 2 corresponds to a straight line with a slope of n. As seen in Fig I, the data of French and the 600°C data of Walker can be represented by straight lines. However, the 500 and 7c0°C data of Walker give curved lines and the average slope of his 500°C line is very different from the slope of the line representing French's data for the same temperature. Furthermore the curvature of the 700°C line suggests a tendency for grain growth to stop after 8 hr. If confirmed, this would constitute a definite deviation from Eq 2, not explainable on the basis of the specimen thickness effect found in high purity aluminum.' Walker's specimens were 0.125 in., or 3.18 mm thick, while the deviation occurs at a grain size of approximately 0.4 mm. A further point of divergence arose recently, when J. E. Burke suggested4 on the basis of Walker's data, that, instead of Eq 2, grain growth in 70-30 brass follows the equation D - D, = K . tgn Eq 3 Here D, is the grain size as recrystallized at the temperature in question. Although it was possible to show5 that, for pure aluminum, for which isothermal grain growth has been carefully investigated, Eq 3 is incompatible with the experimental facts, the situation remained somewhat obscure with respect to 70-30 brass. In view of the discrepancies between the published data on brass from different

Jan 1, 1949

By David J. Mack

The structures and properties of the copper-aluminum alloys have been the subject of much study since the classic investigation of Carpenter and Edwards1 focused attention on. the engineering utility of these alloys. It was recognized at an early date that the metallographic structures developed in the aluminum bronzes were similar to those developed in steels, both in the annealed and the rapidly cooled state. Most investigators have been concerned with the acicular, martensitic-like structure formed from the 0 solid solution upon rapid quenching; the transformation of the ß under equilibrium cooling to a lamellar eutectoid having been relatively neglected. With the introduction in 1930 by Davenport and Bain2 of the isothermal transformation technique for studying eutectoidal decompositions, a new field was opened. Although an enormous amount of work has since been done on the isothermal transformation of steel, study of structurally analogous systems has been almost totally overlooked. The outstanding exception was the prize-winning paper† of Smith and Lind1ief³ ho investigated the decomposition of the 0 phase in copper-aluminum alloys by isothermal methods. This was followed in 1934 by Wasserman's review' of available information on analogous transformations in eutectoid alloys. Since that time no comprehensive study of isothermally transformed eutectoids analogous to steel has appeared, although many valuable contributions have been made to an understanding of the structures developed in such systems. Important papers have been published by Kurdjumow, Gridnew and co-workers, Obinata,18.'9 Greninger,20.21 and Others. The work to be described in this paper was an outgrowth of preliminary studies on the isothermal transformation of a entectoid aluminum bronze, after it became apparent that the alloy under study was reacting somewhat differently than the similar alloy used by Smith and Lindlief. Preliminary Experiments The material used in this study was a high purity aluminum bronze especially prepared by Ampco Metal, Inc. It analyzed: Copper—88.07 pet, Aluminum—11.89 pct, Iron-—0.02 pet, Manganese—-.OI pct, Others—Balance. Although some disagreement exists on the exact composition of the eutectoid, this alloy was believed to be of essentially eutectoid composition even though some pro-eutectoid* delta particles existed in the microstructure of furnace cooled specimens. Specimens transformed isothermally at temperatures slightly below the eutectoid showed relatively large amounts of pre-eutectoid delta, but as will be shown later, this results

Jan 1, 1949

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By T. R. Graham, J. R. Long

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By J. R. Long, T. R. Graham

This report is concerned with part of a series of investigations carried on by the Federal Bureau of Mines on alloys, particularly nonferrous alloys, made with electrolytic manganese. A broad general program instituted after commercial quantities of electrolytic manganese became available was necessary in order to compare the effects of electrolytic manganese with those of the ordinary commercial grades. Representative analyses of these two materials show the commercial manganese metal to contain up to 2 per cent iron, a maximum of I per cent silicon and 0.06 per cent carbon, while the electrolytic manganese rarely exceeds 0.01 iron, 0.02 sulphur, with no silicon or aluminum. In the literature, the emphasis has been largely on high-strength casting alloys containing up to 5 per cent manganese, and few data are available on wrought manganese alloys. These factors, coupled with the strategic position of copper and zinc, have given impetus to the Bureau's War Research Program for the development of alloys containing nonstrategic manganese for the purpose of supplementing or providing alternates for the more strategic metals. The alloy reported here was studied, along with several other ferrous and nonferrous alloys, as possible cartridge-case material, and was chosen after a review of the properties of the ternary alloys of copper-manganese-zinc. Preliminary Work In a cursory survey of this system, alloys ranging from 60 to 95 per cent copper, o to 50 per cent manganese, and 5 to 40 per cent zinc were investigated. The alloys containing 60 per cent copper were found to fall into the two-phase alpha plus beta region of the system, and since those containing 70 per cent would not permit a saving, only alloys containing 65 per cent copper were considered. The tensile properties of these 65 per cent alloys are plotted in Fig. I as a function of manganese content for annealed material and for four conditions of cold-work In the annealed condition the increases in strength and decreases in elongation are minor up to 15 per cent manganese; beyond this, the changes become more significant. In the cold-worked condition, the first 5 to 10 per cent of manganese appears to have the greatest strengthening effect, the rate of increase dropping off as the manganese increases beyond this amount. These effects are more pronounced with moderate than with severe cold reduction. It is also interesting to note that while the elongation of annealed material drops regularly with increasing manganese, the elongation in the cold-worked state is relatively little affected by increasing manganese content, particu-

Jan 1, 1944

By T. R. Graham, R. G. Feustel, J. R. Long, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By J. R. Long, T. R. Graham, R. G. Feustel, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By H. l. Burghoff, J. S. Porter

This paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial Practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 90 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about Io per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrettl states the fiber axis of annealed 70-30 brass wire to be [111], with some indication of [IOO] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. Material and PRocedure All the wire for the investigation was processed from one portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02, nickel; 29.83 zinc (by difference). The billet section, 8 in, in diameter, was extruded hot to 3/4-in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 87s°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By H. l. Burghoff, J. S. Porter

This paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial Practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 90 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about Io per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrettl states the fiber axis of annealed 70-30 brass wire to be [111], with some indication of [IOO] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. Material and PRocedure All the wire for the investigation was processed from one portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02, nickel; 29.83 zinc (by difference). The billet section, 8 in, in diameter, was extruded hot to 3/4-in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 87s°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947