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By M. C. Udy, P. C. Rosenthal

The use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace. The present study presents the results of a systematic survey of the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels. Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. Experimental Work Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. Table i.—Nominal Composition of the Two Base Alloy Steels composition. Per Cent. steel Mn Si Ni Cr Xi-Cr-Mo Wrought 0.28-0.70-0.15-o.45—o.45-0.32 0.90 0.25 0.55 0.55 Cast 0.28-0.70-0.35-0.45-o.45- 0.32 0.90 0.45 0.55 0.55 hln-&lo Wrought 0.28-I .go-o.0.15-0.32 1.70 0.15 Cast o. 28- I.40- 0.35- 0.31 1.70 0.45 a Sulphur was 0.040 per cent maximum and phosphorus 0.030 per cent maximum. Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions was prepared with boron additions in amounts of o.oo15, 0.003, and 0.006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two commercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120. Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel. scrap were used for melting stock. Deoxidation was carried out in the furnace with 0.10 per cent aluminum. The aluminum addition was

Jan 1, 1948

By M. C. Udy, P. C. Rosenthal

The use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace. The present study presents the results of a systematic survey of the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels. Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. Experimental Work Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. Table i.—Nominal Composition of the Two Base Alloy Steels composition. Per Cent. steel Mn Si Ni Cr Xi-Cr-Mo Wrought 0.28-0.70-0.15-o.45—o.45-0.32 0.90 0.25 0.55 0.55 Cast 0.28-0.70-0.35-0.45-o.45- 0.32 0.90 0.45 0.55 0.55 hln-&lo Wrought 0.28-I .go-o.0.15-0.32 1.70 0.15 Cast o. 28- I.40- 0.35- 0.31 1.70 0.45 a Sulphur was 0.040 per cent maximum and phosphorus 0.030 per cent maximum. Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions was prepared with boron additions in amounts of o.oo15, 0.003, and 0.006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two commercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120. Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel. scrap were used for melting stock. Deoxidation was carried out in the furnace with 0.10 per cent aluminum. The aluminum addition was

Jan 1, 1948

By A. K. Jena, M. O. Bever

The thermodynamic behavior of dilute solutions of copper, silver, and gold in liquid tin is not explained by current solution theories.1-3 The relative partial gram-atomic enthalpies, or heats of solution, of silver, gold, and platinum in liquid lead at 623°K have been measured in the investigation reported here. Their interpretation requires a modification of the regular-solution theory although lead-rich solutions may be expected to be simpler than tin-rich solutions. The liquid metal solution calorimeter used has been described.4 At the start of a run the bath consisted of 621 g of reagent-grade lead. Several calibrating additions of lead were made during a run; a value of 3.48 kcal per g-atom5 was taken for H623°K - H273°K Two runs were made with each of the solutes silver, gold, and platinum. Annealed wire samples of 99.999+ pct purity were used. Four to six samples each weighing 0.5 to 1,0 g were added from 273°K to the bath at 623°K and the associated heat effects were measured. The samples dissolved in approximately 3 min. No serious experimental difficulties were encountered. The heat effects of the additions in a run plotted against the average atom fraction of solute before and after each addition314 were linear functions of the concentration in lead of silver, gold, and platinum, respectively. By subtracting the difference between the heat contents of a solute element at 623° and. 273°K5 from the measuredheat effects, the partial gram-atomic enthalpy relative to the solid solute was obtained. The relativ: partial gram-atomic enthalpy at infinite dilution and the concentration dependence of the partial gram-atomic enthalpies obtained from the plots of vs atomic fraction x are listed in Table I. The relative partial gram-atomic enthalpy at infinite dilution of silver in lead of 5.46 kcal per g-atom at 623°K compares with values at 723°K of 5.74' and 5.765 kcal per g-atom. These data yield a temperature coefficient of 3.0 cal per g-atom-OK. The partial gram-atomic enthalpy at infinite dilution of gold in lead at 623°K is 0.89 kcal per g-atom compared with 0.85 kcal per g-atoms (obtained by extrapolation) and 0.95 kcal per g-atom.5 By combining these values for 623°K with those for several other temperatures5" the temperature coefficient of was found to be 3.2 cal per g-atom-OK. No thermodynamic data are

Jan 1, 1968

By Owen F. Devereux

Two discrete types of microstructure me seen in cermets formed by the reaction: 4Al (liquid) + 3SiO2 (glass) — 2A12O3(a) + 3Si (solid) Relatively coarse-grained macroscopically isotropic specimens resulted from reaction with aluminum containing appreciable silicon, while macroscopically anisotropic fine-grained specimens were formed by reaction with aluminum low in silicon. Optical microscopy, electron microscopy, and X-ray diffraction suggest that the anisotropic material contains gross areas in which submicroscopic grains of a A12O3 are oriented along radial lines drawn from the specimen surface. These lines are presumed to originate at defects in an otherwise protecting surface layer. A unique cermet is formed by the reduction of high-silica glass by molten aluminum according to the reaction: 4A1 (liquid) + 3SiO2 (glass) — 2A12O3 (a) + 3Si (solid) The free-energy change accompanying this reaction is -150 kcal at 800°C; the volume change (volume of A12O3 and silicon minus volume of SiO2) is +6 pct. The reaction product, however, contains aluminum metal as well as Al2O3 and silicon because some of the product silicon is dissolved in the aluminum bath and is replaced by aluminum in the structure. The product is a hard gray solid that retains the external dimensions of the original silica article. The system has been studied in the past, the investigations culminating in patents to George1, 2 and Saw-chuk., The former emphasize that this reaction is but one of a relatively broad class of such systems, while the latter demonstrates that a marked improvement in the gross physical properties of the cermet can be obtained by dissolving appreciable quantities of silicon in the aluminum reactant. The system has also been studied by workers at Rolls Royce Ltd.,4-6 who have patented the addition of small quantities of arsenic, antimony, bismuth, or phosphorus to the reactant bath to SO impede the reaction that glass fibers may be metal-coated by immersion in molten aluminum.

Jan 1, 1969

By S. F. Frederick, W. A. Bailey

The relationship between microstructure and mechanical properties of cast 356-type aluminum alloys was studied to determine the cause of the variations in properties resulting from differences in solidification rate. It was found that variations in strength are a consequence of variations in ductility and that ductility is inversely proportional to the dendrite cell size. A mechanism is proposed to account for this correlation based on the fracture strain of the inter-dendritic silicon particles and the differential strain across dendrite cell boundaries. IT has long been assumed that permanent mold castings of aluminum are superior to sand castings because of their finer grain structure and reduced porosity.' A systematic variation of static properties was noted during unpublished studies of fatigue-strength variations with solidification rate of A356-T6. Of particular interest was the observation that for a given composition and heat-treatment, both ductility and the ultimate strength increased with higher solidification rate. Because the A1-Si system forms the basis of many alloys used for castings and welding wire, a study was initiated to determine the details of how higher cooling rates improved mechanical properties of these alloys. The results of this study are presented here. EXPERIMENTAL PROCEDURE Specimens were prepared from 356-T6 to supplement the A365-T6 alloy data from earlier studies. This allowed a comparison of behavior of alloys with substantially different strengths but with only small differences in alloy composition. The composition and heat treatment of both alloys are given in Table I. The specimens were cut from a chill plate casting,' which is a 6 by 9-in. plate, 1 in. thick, which has one end heavily chilled, and a large riser at the other so that solidification is essentially unidirectional from the chill end to the riser. Although not measured here, solidification times measured on similar specimens by embedded thermocouples are a few seconds at the chill end and up to 5 min near the riser. Specimens were obtained by cutting slabs from the plate, parallel to the chill; these represented different cooling rates, with essentially the same composition. For the tests, either 0.125 or 0.250-in. thick slabs were cut for standard 2-in. gage length specimens. The thicker specimens were tested to failure at 2000 lb per min while the thinner specimens were tested in an Instron machine at a constant cross-head speed of 0.02 in. per min. These thin specimens were intended for trans- mission electron microscopy. Some thin specimens were tested to failure while the remainder were given various amounts of prestrain. Dendrite cell sizes were measured by the linear intercept method on photomicrographs at either X100 or X50, depending on the cell size. It was assumed that the dendrite cells were outlined by the silicon particles. Determinations were made on two mutually perpendicular planes and an rms average taken. Electron fractographs of representative tensile specimens were made in the conventional manner using the two-stage replica technique.3 Samples for transmission electron microscopy were prepared by chemical milling followed by electropolishing. RESULTS AND DISCUSSION The results of the tensile tests and the dendrite cell-size determinations are given in Figs. 1 and 2. All data show the same trends, namely, a decrease in ultimate strength and elongation with increasing distance from the chill (and solidification time), and a corresponding increase in dendrite cell size. The yield strength remains essentially constant. The constancy of the yield strength was particularly significant since it indicated that variation in the solidification rate does not affect the stress required to initiate plastic flow. By plotting true stress-true strain curves as in Fig. 3, it can be seen that both

Jan 1, 1969

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

ONE of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing of the A.S.T.M., 1938. The work of Mann,1 Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserve especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by [P OL, plotting So = Ao as a function of eo = Lo] where A o and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors' It was shown that the true physical behavior of the material in the tension test could best be represented [by plotting the average true stress, S = P as a function of e = q' = log o = log Log] where P, A, L, S, e, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximum load point to fracture. The construction of such- curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain difficulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece

Jan 1, 1941

By W. C. Ellis, E. S. Greiner

METALLIC titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arkel2 and Fast3 prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kroll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper: was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725°C5 it may be classed as a light metal since the specific gravity is 4.5 g per cc-1. The crystal structure is close-packed hexagonal from room temperature t0 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat8 electric resistance9 and thermoelectric force10 at temperatures near 890°C. It is reported11 that annealed titanium has a tensile strength 0f 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between - 200 and 1000°C have been determined. MATERIALS For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was lade from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at 1000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was lade from a rod of titanium, 0.19 in. in dial, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table I. Oxygen and nitrogen which were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1948

By A. A. Smith, J. S. Smart, A. J. Phillips

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By A. J. Phillips, A. A. Smith, J. S. Smart

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

Executive HOWARD N. EAVENSON, Chairman FREDERICK M. BECKET EDGAR RICKARD ERLE V. DAVELER WILLIAM WRAITH Finance HENRY KRUMB, Chairman PAUL I). MERICA J. V. W. REYNDERS H. G. MOULTON, Consultant Admissions JOHN M. LOVEJOY, Chairman GEORGE D. BARRON DONALD M. LIDDELL ELI T. CONNER WILLIAM W. LYNCH Alternates WM. H. BASSETT, JR. L. B. LINDEMUTH W. A. SINSHEIMER

Jan 1, 1934

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By E. N. Silverman

Mixtures of' MnS, ZFeO-SiO,, ZMnO.SiO, FeO, and MnO were prepared synthetically and used to study the planes ZFeO. Si0,-ZMnO.SiO,-MnS, FeO-MnO-MnS, and Fe0-MnO.Si0,-MnS in the quaternary system. Because the oxides and silicates studied flux MnS, inclusions in this system are partly liquid during rolling. Also, oxygen can modify subsurface inclusions through the reaction MnS + FeO—FeS + MnO during the soaking of ingots and the reheating of blooms and billets. NONMETALLIC inclusions in steel have long been a subject of study and conjecture because the properties of many steels are known to be affected by the the kind and amount of inclusions present. In free-machining steels, the type of inclusion present has a direct bearing on their machinability; in other steels, cleanliness is important and metallurgists direct their efforts at reducing the amount of non-metallic inclusions. Thus, the accumulation of knowledge about the formation and behavior of inclusions during all stages of steelmaking and processing should aid in improving the quality of steels and decreasing the production costs resulting from rejections. Previous studies of inclusions have contributed greatly to our understanding. The investigators have generally examined inclusions in finished steel. Boulger, Moorehead, and Garvey1 found that in Bessemer steels, low silicon contents results in globular sulfide inclusions with attendant high machin- ability ratings. Van vlack2 also found that low silicon contents favor inclusion morphology that contributes to high machinability ratings. Boquist and Stoll* found that silicon content affected sulfide inclusions and machinability of blooms, billets and bars more than did the finishing temperature in the range between 1775° and 2075°F. Carney and Rudolphy3 studied the distribution of sulfur, manganese, silicon, and carbon in a commercial ingot of resulfur-ized steel and found that silicon was concentrated near the bottom. This helped to explain why bottom cuts had poorer machinability. Klinger and Koch4 developed techniques for extracting inclusions from steel, and the technique devised by Gurry, Chris-takos, and stricker5 for extracting carbides can also be adapted to the study of inclusions. A different approach to the study of inclusions in steel consists of synthesizing the constituents that form inclusions and determining the phase eauilibria in the system that contains the constituents. The resulting phase diagrams can then be used to determine the effect of the various constituents upon each other. In this way, it becomes possible to under-

Jan 1, 1962

By A. N. Holden, W. E. Seymour

DURING the last several years, the U-Zr system has been studied at many laboratories as one of the research programs sponsored by the Atomic Energy Commission. The equilibria in part of this system have been difficult to determine, although the phase diagram from 0 to 60 atomic pct Zr has been established with reasonable certainty. Existing diagrams of the system vary appreciably beyond 60 atomic pct Zr, particularly with regard to the existence of an intermediate phase. Most existing diagrams show a transformation or reaction horizontal near 600°C. In 1955, a collection of uranium phase diagrams' was prepared at the Battelle Memorial Institute and the U-Zr diagram in that collection contained a questionable region in the vicinity of 60 to 80 atomic pct Zr. Summer-Smith" has published a phase diagram of the system that shows no intermediate phase. Summer-Smith did his work with powders and found only the uranium and zirconium eutectoid mixture from X-ray patterns of material annealed below 600°C. Mueller3 at Argonne National Laboratory did similar work with filings, and he found that initially there was a pattern of an intermediate phase, but on long-time annealing

Jan 1, 1957

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

Solid-solubility limits at 1500°, l000q and 500°C for carbon, nitrogen, and oxygen in high-purity tantalum were determined by X-ray lattice-parameter methods. For carbon, the solubility was found to be 0.17 at. pct at 1500°C, and less than 0.07 at. pct at 1000°C. A nitrogen solubility of 3.70 at. pct at 1500° C decreases linearly with temperature to 2.75 at. pct at 1000°C, and 1.8 at. pct at 500°C. In the case of oxygen, the solubility was found to be 3.65 at. pct at 1500°C, 2.95 at. pct at 1000°C, and 2.5 at. pct at 500°C. The phases Ta2C, the low-temperature modification of Ta205, and Ta,N of unknown composition but which has a superlattice structure based upon the original bcc tantalum lattice have been identified as the initial precipitates in the respective systems. Metallographic methods were employed to verify the X-ray analyses. The etching behavior of Ta is discussed in terms of lattice i?rzperfections and precipitate phases. The excellent fabricability, high melting point, and nuclear properties of tantalum are responsible for interest in this refractory metal. Data on the solid solubility of the interstitial elements (oxygen, nitrogen, and carbon) in tantalum and on the precipitate phases are somewhat limited. The significant contributions are discussed below. Because the purity of electron-beam melted tantalum (only recently available) is considerably higher than that used in previous studies, the present investigation was initiated. Gebhardt et all-3 have investigated the tantalum-oxygen and tantalum-nitrogen systems with particular reference to the changes in physical properties and to the rates of reaction between these gases and the metal. The solubility of oxygen in tantalum was reported2 to be 3.7 at. pet at 1500°, 2.3 at. pet at 100O°C, and 1.4 at. pct at 750°C. Schonberg4 reported that several oxide phases (Ta40, Ta,O, TaO and Ta,05) exist while X-ray studies by Gebhardtl showed only two oxides, Ta,05 and an unidentified phase which was associated with a platelet-type precipitate. La-gergren and Magneli,' however, questioned the existence of compounds other than the two allotropic modifications of Ta,05 for the tantalum-oxygen system. In the case of nitrogen, the solubility was estab- lished by Gebhardt3 to be of the order of 7 at. pct at 1800°c. The solubility was reported to decrease rapidly with temperature, and, although no limits were established, a precipitate phase was observed by Gebhardt except when the high-nitrogen specimens were cooled very rapidly from the reaction temperature of 1800c. He reported the initial precipitate phase to be a tetragonal distortion of the bcc tantalum lattice while Schonberg6 reported the phase lowest in nitrogen Jo be a cubic super-lattice with a cell size of 10.11 A. Two other nitride phases, Ta,N and TaN, were reported; these appear to be isomor-phous with the carbides of tantalum. The tantalum-carbon system was investigated by Ellinger7 and by Lesser and Braurer. Two compounds, Ta,C and TaC, were reported to exist, each with a range of composition. The solubility of carbon in tantalum was found to be practically nil at all temperatures. Thus, of the interstitial elements which are present in small amounts in high-purity tantalum, carbon might be expected to form precipitates. The present investigation was initiated to obtain additional data on the solid-solubility limits of these interstitials at 1500°, 1000°, and 500' with particular emphasis on the distribution and the identification of the precipitate phases. EXPERIMENTAL WORK AND RESULTS In the present investigations of the solid solubility and of the precipitate phases in the systems tantalum-nitrogen, -oxygen, and -carbon, high-purity tantalum was reacted with high-purity gases, homogenized at 1800°c, and annealed at and quenched from 1500°, 1000,

Jan 1, 1962

CAPTAIN JOHN H. BALLAMY John H. Ballamy, Captain on the Regimental Staff of the 103d Engineers, was killed near Fismes, on August 9, 1918. Captain Ballamy was born at Plymouth, Pa., in 1886 and graduated from the High School of that town in 1903. In the following year he began work as a coal miner, and at the same time began the study of mining engineering in the evening and any other spare time. He continued this diligent and energetic practice for many years. For sixteen years he continued in the employment of the Delaware, Lackawanna & Western Railroad Company's coal mining department, first as a practical miner, next as rodman on the survey corps, of which he soon became chief, then draftsman and mining engineer in the company's office. In January, 1916, he was promoted to the position of district engineer in charge of mining engineering work. He became a member of this Institute in September, 1917. CAPTAIN JOHN H BALLAMY. Captain Ballamy's military experience began at the same time as his engineering practice. He was a charter member of Company A, Engineers, N. G. P., which was organized ten years ago. He saw service on the Mexican border as First Lieutenant of this Company, and remained in that position until November, 1916. In July, 1917, he was again called into service and was sent to Camp Hancock, Ga., with the 103d Regiment of Engineers. Before joining this regiment he attended a school for officers at Fort Sill, Okla., where he received special training in field fortifications. In December, 1917, he was commissioned Topographical Captain on the Regimental Staff, and in April, 1918, preceded his regiment by about six weeks to France, where he again attended an officers' training school. He rejoined his regiment on July 15, near Chateau Thierry and was killed near Fismes on August 9, 1918.

Jan 11, 1918

By F. J. Williams

BARITE, naturally occurring barium sulphate, is the chief barium mineral that is produced commercially. Barite is also called "barytes," "heavy spar," sometimes "baryta" and, locally in Missouri, "tiff." Pure barite is white, opaque to transparent. It crystallizes in the orthorhombic system, frequently with twinning. Impurities cause a wide variation in color, commonly buff, gray and white with irregular reddish iron stains. Less frequently found are shades of yellow, green, blue, brown, and black. The rock is brittle and breaks with an uneven fracture, although specimens from some of the residual deposits, particularly in Missouri, appear to have a cleavage due to the separation of the different layers of deposition. The hardness varies from 2.5 to 3.5 on Mohs' scale and different localities are said to produce either "hard" or "soft" barite. This generally refers to the ease of grinding of the product. The specific gravity of pure barite is 4.5 and this will vary downward, depending on the impurities present. The mineral has a white streak and a pearly to vitreous or sometimes stony luster. Pure barite contains 65.7 pct BaO and 34.3 pct SO3. Witherite, native barium carbonate, is not mined in the United States at the present time although a number of occurrences have been reported. A small quantity of witherite has been removed from a mine at El Portal, California, but the area high in witherite was small and soon depleted. The bulk of the deposit is predominantly barite. Great Britain is the world source of witherite and small quantities are imported into the United States. DISTRIBUTION OF DEPOSITS Occurrence of barite is widespread; it has been reported on all the continents and in all the major countries of the world. Deposits vary from those containing millions of tons down to scattered rock fragments

Jan 1, 1949

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of' very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of' the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By M. H. Richman, W. D. Sproul

THE indexing of a field-ion micrograph is in many cases similar to the indexing of the poles of a stereo-graphic projection.* If one has a standard projection as a guide, the task of indexing is relatively simple. In this way, field-ion micrographs of bcc and fcc wires have been oriented from projections available in most any text on X-ray diffraction. These books always illustrate the projections for the bcc and fcc structures and even for a particular hcp structure. There is no "standard" hcp projection because the angles between planes depend on the c/o ratio of the unit cell. In order to index field-ion micrographs of hcp metals, one must compute the angles between various planes—a rather laborious task. In recent work,, we have had to identify the structure and index the orientation of field-ion micrographs of the compounds WC and W,C. To overcome the problem of computing angles by hand or calculator, a program was written in Fortran lV for use on the IBM 360, Model 50 which will compute all angles between planeswith indices (hlklll) and (17,k,l2) in the range from (447) to (444) for any given c/o ratio. The program, which is more specific than that of Camp and clum, was so written as to take advantage of the multiplicity of the hexagonal system, and, for the limits defined above, only 26,649 values out of a possible 265,721 values had to be computed. This is a 90 pct saving in time (and cost) and was accomplished in the following way. Because the lattice parameters of the hexagonal crystal system are defined such that: a = b * c [1] the I index does not enter into the multiplicity (i.e., it cannot be transposed with the h or k indices), and all possible values of h and I, from 4 to 4 must be used—a total of eighty-one combinations. The index h2 varies the most—it must assume values from - Ill,: to 3Ihl. The indices kl and k2 are always equal and vary

Jan 1, 1969

By W. F. Holbrook

In a previous paper1 a method for the measurement of the comparative desulphurizing power of slags was described and data were presented covering the range of likely slags containing up to 10 per cent MgO. In the present work the range is extended to include slags containing up to 20 per cent MgO, and the effect of temperature on 5 per cent and 15 per cent MgO slags over the range 1475' to 1525' C. is included. The method used was that described in the previous paper except that some of the temperature measurements were made with a noble-metal thermocouple instead of a tungsten-graphite thermocouple. Twelve-gram charges of 0.8 per cent sulphur-metal and 5-gram charges of slag were subjected to heating for 30 min. at a prescribed temperature. The charges were analyzed for sulphur content. For purposes of comparison, desulphurizing power is defined as the ratio of the percentage of sulphur found in the slag to that found in the metal. Six slag and metal charges were made coincidentally in 5/8in. holes in a section of an electrode graphite rod. One slag and metal charge was used as a control by means of which adjustment in the desulphurization value could be made for small variations in temperature and other factors. For convenient presentation of the data, the slags are arranged in groups in each of which one of the four main slag components is constant. Thus, the 15 per cent MgO slags are presented separately from those containing 20 per cent MgO. Slags with Magnesium Oxide Constant 15 Per cent Mg0.—The data on slags containing 15 per cent MgO cover a composition range of 24 to 50 per cent SiO2, 5 to 27 per cent A1203 and 24 to 53 per cent CaO. Variation in composition has been in steps of 2 per cent over much of the area. Because the change in desulphurization power is generally gradual with gradual change in composition, certain sections have been covered in steps of 4 per cent and even

Jan 1, 1938