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By H. C. Fiedler

SILICON-IRON strip with a cube-on-edge secondary recrystallization texture is made commercially as thin as 10 mils. With inclusions present to inhibit normal grain growth, a few grains, and these have the (110)[001] orientation, grow very large at the expense of the matrix grains. In the absence of inclusions, only normal grain growth occurs and the texture is not as strong as when it is developed by secondary recrystallization.1 Strip for use at frequencies of 400 cps and higher is made in thicknesses of 1, 2, and 4 mils by a process developed by Littmann.2 Attempts to develop a strong texture in these thin gages by the same methods as were used for the 10 mil and thicker strip were unsuccessful,2 and Littmann's solution to this problem was to cold roll the grain

Jan 1, 1963

By J. T. Lapsley, I. I. Cornet, A. E. Flanigan, R. Hultgren, J. E. Dorn

With the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that procedures of heat treating common magnesium casting alloys be investigated systematically. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. Research on the solution heat treatment and aging of magnesium alloy AZg2, (formerly ASTM No. 17; also known as Dowmetal C or AM26o) which was done under "Restricted" Project NRC-2I, in 1942-1943, and reported in detail in a final report to the OSRD on September 3, 1943, is the basis of this paper, which has been released for publication by the OSRD. American experience with magnesium alloys prior to World War II was limited, although some of these alloys had been in commercial use since 1909. Requirements of the aircraft industry for light alloys made it imperative to understand and utilize the advantageous strength-weight properties of magnesium castings. Magnesium casting alloys are commonly solution heat- treated to increase their ultimate tensile strength and ductility; this treatment may be followed by an age hardening at elevated temperatures, which raises the tensile yield strength but diminishes the ductility. In the present investigation, AZp was studied to determine the effects on properties of various solution heat treatment and aging schedules. The principles of heat treatment of magnesium alloys are the same as for other non-ferrous alloys. The alloy studied, AZp, has a nominal composition of 9 pct aluminum, 2 pct zinc, and minor constituents. Fig I shows, by the projection of isothermal sections on the concentration plane, the solubility surface1 of the ternary magnesium-rich solid solutions as determined by X ray 'analysis. From this figure it may be seen that above approximately 375°C (707OF), AZp alloy is a single phase alloy at equilibrium; below this temperature the equilibrium condition is a two phase alloy. The beta constituent which precipitates from the solid solution exerts a hardening effect. Because the zinc concentration is only 2 pct, ancl because of its solubility relations, AZqz resembles a binary alloy of magnesium with aluminum. The solubility curve1 of Fig 2 shows how rapidly the solubility of the beta phase decreases with decreasing temperatures. Unlike many aluminum alloys, magnesium alloys do not age harden at room temperatures; precipitation hardening of AZ² alloy is performed at about 177°C (350°F). At this temperature about 3 pct aluminum

Jan 1, 1949

By Harmon E. Keyes

Harmon E. Keyes (Chemical & Metallurgical Engineer, Eagar, Ariz.)-Chemical dissolution of chalcocite by acidic ferric sulfate is well known. Resulting elemental sulfur may be oxidized to sulfuric acid by heated ferric sulfate. Laboratory tests at Southwest Experiment Station, USBM, Tucson, generally confirmed stoichiometric relations of 1 part Cu dissolved to 1.750 parts ferric iron reduced, using CP chemicals, dried ore samples, and apparatus cleaned with potable water. Recirculation with open-drainage percolation to increase copper in leaching solvent was followed successfully when appropriate, both in laboratory and Pinto Valley pilot tests. Before 1924 attempts to produce ferric sulfate by aerating ferrous sulfate solution were known. Initial oxidation was satisfactory, but rate slowed below practicality as oxidation progressed and acidity increased. Also, due to hydrolysis of ferric sulfate, a ferric precipitate of hydroxide and basic sulfate resulted. Both laboratory and pilot plant tests gave similar results, regardless of whether CP ferrous sulfate or scrap iron cementation discard solution was used. Rapid oxidation of ferrous hydroxide by air alone is well known to analytical chemists. I demonstrated a process to produce acidic ferric sulfate solutions by precipitating ferrous hydroxide with milk of lime, aerat-

Jan 1, 1973

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.' In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By George S. Rice

THE A.I.M.E. Ground Movement and Subsidence Committee, pro- posed in 1920, held its first technical meeting in February 1923, under the able chairmanship of Mr. H. G. Moulton. The following list of papers and discussions, indicating the scope of the problems and relation to various conditions and method of mining, were given at that meeting by the distinguished mining engineers: J. Parke Channing, on Subsidence at Miami, Arizona; Howard N. Eavenson, on Mining an Upper Bituminous Seam after a Lower Seam Has Been Extracted; J. J. Rutledge, on Subsidence in Two Oklahoma Coal Mines; Benjamin F. Tillson, on Caving Cracks at the Franklin Mine, New Jersey; Dr. F. W. McNair, on the Dome Theory; William Kelly, on disadvantageous effects in Mining and Back-filling Working Upward a Steep-Pitching Iron-ore Bed; Eli T. Conner, on the good results of Back-Filling by Hydraulic Means in Preventing Destructive Subsidence in the Anthracite District; Thomas H. Claggett, on the merit of Systematic Pillar Drawing in Preventing Cracks in an Upper Seam; Henry H. Otto, successful results in the anthracite district in Mining Lower Seams before Upper Seams; Douglas Bunting, on Leading Factors Incident to Successful Mining of an Overlying Seam; Edwin Ludlow, on there being "less damage to buildings when there was complete removal of coal with complete packing than when room and pillar is used without extracting the pillars"; Edward O'Toole on "bumps" in eastern Kentucky mines, which he thought were the result of geologic stresses: H. A. Buehler, on Upheaval of Surface in an Illinois Case in Advance of the Face; and R. Dawson Hall, on The Mechanics of Subsidence from Mining. The author of this paper discussed various kinds of problems of ground movement and subsidence in both metal mining and coal mining; the production of great landslides by workings near an outcrop, as at Turtle Mountain, Alberta, Canada; and general

Jan 1, 1939

Frank Firmstone, Easton, Pa. (communication to the Secretary*) : It may not be amiss to point out that the top-pressure in iron blast-furnaces is largely affected by variations in the temperature of the gas. I find in my note-books, cases in which the pressure was from 9.25 to 9.5 in. of water when the material in the furnace was low (after dinner-hour), which fell to from 8 to 8.5 in., when the furnace was again full, and the gas consequently cooled. The chief cause for this effect is, that, at the higher temperature, there is a decrease in the weight of the gas in the descending-leg of the siphon formed by the down-comer and the chimneys. It does not seem probable that there is any direct relation between top-pressure and quantity of flue-dirt. Top-pressure, at any given moment, measures the " head " necessary to discharge the gas then passing, against the resistances of pipes, valves, etc., in the gas-conduits between the top of the furnace and the mouths of the chimneys, and can be increased at will by closing, more or less, the valves, or dampers, at the stoves and the boilers. The question of relation between top-pressure and flue-dirt can be settled very easily by direct experiment, working alternately with gas-valves open, and partly closed, and noting the top-pressures and the respective quantities of fluedirt collected. The quantities of fine ore blown away, as shown by Mr. Grammer's tables, are astonishing to one who has had no actual experience with Mesabi ore and hard driving. Flue-dirt, in the sense in which he uses the term, was unknown at anthracite furnaces so long as the working was normal; when it did occur, it was always an incident of scaffolding and bad work, and was no doubt caused by an increase in the velocity

Jan 1, 1904

By R. W. Jordan, J. Winter, A. J. Goldman

Kirkendall diffusion of copper and nickel atoms across the bond interfaces, as well as oxygen diffusion in the core to the interfaces, are the mechanisms which control the variation in bond strength with annealing time at 1600°to 1800°F in the cupro-nickel clad copper Mint composite. The unequal mass transfer resulting from the high diffusion rate of copper in cupro-nickel compared with that of nickel in copper caused void formation in the core. Small voids also formed in the cladding after short annealing times. These may have been nucleated by nickel oxide particles which are formed by the dissociation of the cuprous oxide in the core and the movement of oxygen to the cupro-nickel interfaces. The bond strength drops to very low values for annealing time up to 3 hr when the void density is greatest. The increase in bond strength after 16 to 72 hr at 1600°F is a result of the decrease in the void density in the cupro-nickel cladding and the growth of grains across the interface. The void density decrease is attributable to grain boundary diffusion of vacancies to the surface. The abnormally large grains in the copper preclude a similar process from taking place in the core. THE solution to many engineering materials problems that cannot be satisfied by using a single metal or alloy is often attained by combining two or more metals in such a way that each component performs a different function, while the composite meets the overall requirements. The Coinage Act of 1965 authorized a changeover from the traditional 90 Ag-10 Cu dimes and quarters to a bimetallic laminate of 75 Cu-25 Ni clad on a copper core. Economic considerations as well as physical, chemical, and mechanical properties provided a basis for the selection of this composite as a substitute for the silver-bearing alloy. An extensive survey of alloys suitable for use as coinage was prepared by Battelle Memorial Institute for the U.S. Mint.1 It was found that the cupro-nickel/cop-per/cupro-nickel composite satisfied the required color, density, mechanical properties, corrosion resistance, electrical properties, and magnetic properties to make it completely acceptable to the general public and the vending machine industry. This investigation is part of a program to determine the feasibility of reclaiming composite scrap by thermally degrading the bond strength of the cupro-nickel clad copper laminate. The composite exhibits bond degradation and subsequent bond improvement during annealing in the temperature range 1600" to 1800°F. A study of the operative diffusion processes and the resultant structural changes was made in order to explain the observed variations in bond strength with annealing time. EXPERIMENTAL PROCEDURES AND RESULTS Bond Degradation. A measurement of the forces required to peel the cupro-nickel cladding from the

Jan 1, 1969

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By A. R. Elsea, E. E. Fletcher

Cast X-40 alloy with the lowest nitrogen content studied had a 100-hr rupture stress at 1500°F about equal to the reported value for the commercial alloy. Increases in nitrogen content progressively decreased the rupture strength, and with about 0.1 to 0.2 pct N a minimum strength was reached, but there was no accompanying change in microstructure. Further increases in nitrogen resulted in the fomzation of progressively increasing amounts of a lamellar, pearlitic-type structure at the grain boundaries, with accompanying increases in rupture strength, and above about 0.25 to 0.33 pct N, the rupture strength exceeded the normally reported values. Two series of melts representing different melting stocks exhibited minimum rupture strengths at different nitrogen contents. This suggests that some unidentwed trace element not removed by vacuum melting has a strong influence on the response of this alloy to variations in nitrogen content. In a series of melts with manganese contents ranging from 0.6 to 3.2 pct, the material with the lowest manganese content had the highest 100-hr rupture strength at 1500°F. The manganese variations had no appreciable effect on the microstructure. CAST cobalt-base alloys such as X-40* exhibit high strengths at elevated temperatures (1500°F and above), but they also show considerable scatter in high-temperature properties. Since the design of parts for critical applications must be based on the minimum expected properties, this broad scatter appreciably lowers the design strength of the alloy. If the relatively poor properties exhibited by a few test parts from any given group could be improved, the spread in properties would be narrowed, and the design stress could more closely approach the average expected properties. The purpose of this research investigation was to learn what were the causes of these erratic properties and, if possible, to find methods for eliminating them. Earlier unpublished work showed that vacuum melting markedly influenced the high-temperature strength of cast X-40 alloy. There were indications that this behavior may have been the result of changes in the nitrogen or manganese content of the castings. Consequently, in the current investigation, the influence of variations in nitrogen and manganese content on the structure and high-temperature properties of cast X-40 alloy was studied. In this program, X-40 melting stock was vacuum melted to produce a base material that was very low in nitrogen content and in volatile trace elements. Additions were then made to this base material to produce alloys of the desired composition. The metal was cast into investment molds producing coupons which were machined into stress-rupture bars. These bars were subjected to stress-rupture tests and me-tallographic study to determine the influence of changes in analyses (nitrogen and manganese content) on the structure and properties. Material—The melting stock used for these experi-ments was in the form of shot from two master heats of commercial X-40 alloy. Only one master heat was used in a given series of melts. Thus, any differences in structure or properties that showed up in the specimens from a given series would be the result only of the intended variations in composition. The certified analyses of the master heats were as follows: C Mn Si Cr Ni Lot No. 2 0.50 0.71 0.66 25.44 10.53 Lot No. 3 0.54 0.73 0.70 25.95 10.00 W Fe Co P S Lot No. 2 7.45 1.34 Bal. 0.011 0.013 Lot No. 3 7.58 1.53 Bal. 0.005 0.016

Jan 1, 1960

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1' and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,'' by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.'= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1' and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,'' by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.'= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By R. C. de Lange

An improved replica technique is developed for a nondestructive study of the nucleation and growth of fatigue cracks. Three different growth stages of a fatigue crack were observed. An initial stage of high growth rate is followed by a long period of very slow growth, until finally a third period of high growth rate leads to fracture. THE metal-fatigue process is of a very complex nature. The experimental approach towards fatigue is susceptible to many minor influences which, together with the unavoidable scatter in testing results, makes the interpretation a matter of extreme care. The generally accepted fact that, in a homogeneous material, the fatigue cracks start at a free surface indicates that surface studies may contri-but in an essential way to a better understanding of the fatigue mechanisms. Indeed metallographic observations of the fatigue phenomena have been very fruitful in the last decade. The study of extrusions, intrusions, and persistent slip bands has contributed much to the present knowledge of the early processes in fatigue.' The drawback of the current metallographic techniques lies in the fact, however, that either observations of fatigue phenomena had to be made in a destructive way after an only partly executed test or a sequence of observations on the same test bar was only possible on notched specimens.2 4 In both cases an uncertainty exists as to the nucleation and growth of the fatigue crack in an unnotched test bar, where the crack can start at any place of a large area and develops in a test bar, which is macroscopically

Jan 1, 1964

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By C. Ernest Birchenall, Robert F. Mehl

Application of diffusion laws in the customary form to experimental studies in binary metallic solid solutions has shown the diffusion cocfficient to vary with concentration for all systems investigated. The factors determining this variation have not been ascertained. However, the question of whether the diffusion coefficient would become a constant, independent of concentration throughout a single phase if the concentration gradient in the diffusion equation were replaced by an activity gradient has been an attractive subject for speculation. Wagner¹ derived an expression for the force acting on a diffusing particle in terms of the chemical potential. This was also the approach chosen by Jost2 in his monograph. From a somewhat different point of view, Eyring3 and his co-workers have used activity gradients when dealing with diffusion in concentrated nonideal solutions. The only actual test with experimental data is that given by Darken,4 though this is more qualitative than quantitative. Many others opposed the application in any way of thermodynamic concepts to kinetic phenomena, including diffusion processes. A rigorous examination of this principle requires good data expressing the relationship between activity and concentration for solid solutions for which reliable diffusion work has been done. The literature provides such information only for the interstitial solution of carbon in gamma iron (austenite) and for the substitutional copper-zinc solutions (alpha brass). Activity data for carbon in austenite at 800°C and 1000°C are available from the recent work of Smith5 on the equilibrium of hydrogen-methane and carbon monoxide-carbon dioxide mixtures with gamma iron. Combining these with the diffusion studies of Wells and Mehl6 makes possible a quantitative test for this interstitial solid solution. The vapor-pressure determinations for zinc over brass by Hargreaves7 allowed the calculation of activities in this system over a wide range of temperatures and concentrations. Extensive investigation of diffusion in this substitutional solid solution has been carried out by Rhines and Mehl.8 Activities in Brass9 If the vapor phase of zinc is assumed to behave as an ideal gas, any solid or liquid solutions that are in equilibrium with the same partial pressure of zinc at the same temperature have the same thermodynamic activity of zinc. In order to assign a numerical value to the activity azn, it is necessary to choose some standard reference state to which an activity value of unity is arbitrarily assigned. It is customary to choose the liquid or solid state of the pure material. Then azn is defined numerically by

Jan 1, 1947

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By John Wulff, Richard P. Seelig

The importance of the pressing operation in the forming of articles by powder metallurgy depends to a great extent on the type of product to be made. While in some few cases the pressing is merely a means of compacting loose powder particles into a solid mass preliminary to a sintering treatment, in most applications it constitutes a molding operation with the purpose of shaping the raw material in powder form into a certain predetermined, accurately defined part not altered in shape by subsequent sintering. In still other cases, no pressing at all but sintering in molds gives useful articles. A limited number of products are made by the simultaneous application of pressure and heat. The factors that control the product of the pressing operation are raw material, lubricant, type, size and shape of die and compact, magnitude and time of application of pressure, as well as temperature of pressing. All such factors need to be controlled; yet, depending on the function of the pressing operation, greater emphasis may be placed on processing factors other than the pressing operation. In any complete discussion of pressing, subsequent sintering cannot be disregarded. For the sake of brevity, the present paper has been limited to the mechanics of pressing and only occasionally refers to sintering. For the same reason, hot-pressing has been omitted as beyond the scope of this paper In any survey of the literature on the pressing of metal powders, the 1938 paper of Balshinl on the theory of the process of pressing deserves mention. The first attempts at an interpretation of pressing phenomena were made by Balshin' and RakovskL2 The experimental results of both are of great interest. Since the experimental results are not described, the work was repeated, using our own interpretation of the possible techniques, and is reported in the following pages. The basic theory of Balshin,' based on a hydro-dynamic analogy, however, leads to hut another way of plotting density and pres- , sure against height of a pressed compact. Since it does not give any new insight into the phenomena, nor account for the influence of side-wall friction, a discussion of the theory has been omitted from this paper. Density Gradients in Compacts The process of pressing metal powders in a die (disregarding for this consideration the powder filling and ejection operations) may be divided into three phases: (I) packing, (2) elastic and plastic deformation, (3) cold-working with or without fragmentation. It must be emphasized that these three steps do not follow each other in sequence; on the contrary, in practice

Jan 1, 1946

By R. E. Rick-Secker, W. M. Baldwin, R. McC. Baker

The development of residual stress in strip during rolling has not been systematically studied. A few scattered papers1 -3 mention the existence of residual stresses in rolled strip or touch upon some of their consequences,4 but there is no report of experimental studies in the literature describing the effect of roll diameter, strip thickness, reduction per pass, metal or metal temper on the magnitude of residual stresses developed in strip. A knowledge of the effect of these factors is of utmost importance since the present trend in some mills to roll thicker castings brings the rolling operation directly into that set of conditions which, as will be brought out in the present paper, can develop residual stresses of a high order of magnitude. Fundamentally, residual stresses are developed when a metal is inhomogeneously unloaded from a plastic stress state. A quantitative treatment of the problem requires a reasonably complete understanding of both the plastic stress state existing in the metal during deformation and the elastic stress state that would exist in the metal if the metal deformed as a perfectly elastic body. Our knowledge of either state during rolling is so meager that we can make no more than certain limited predictions. The external stress state* operating between the roll and the metal consists of Fig i—External stress state operating on metal being rolled (after siebel and LUEG5) compressive stresses acting almost perpendicularly to the strip surface but varying in intensity both across the width of the strip and along the length of contact between the roll and the strip. An example of such a stress distribution is shown in Fig I. The nature of the internal stress state, produced by this distribution, is not known. Various investigators,5-7 however, have felt that a qualitative similarity must exist between the internal stress state so produced and that produced in a wide strip that is compressed between two flat-nosed punches. In the latter case the external stress state is represented by a uniformly distributed compressive stress acting per-pendicularly over the face of the tool. The

Jan 1, 1949

By M. E. Nicholson

IT has been suggested by a number of investigators, I including Hume-Rothery and Raynor,' that certain intermediate phases in metal systems take on interstitial crystal structures because of an appropriate ratio of radii of the two atoms. If the size factor is an important parameter in determining whether or not an intermediate phase will have an interstitial structure, then it would appear reasonable that the relative sizes of interstitial atoms should have a direct relation to their solubilities in interstitial compounds. It was on such a basis that Petch,' in his discussion of the cementite structure, concluded that nitrogen is the only possible element which could replace carbon. Recent X-ray studies by Jacka indicate that the solid solubility of nitrogen in cementite is negligible. If this is the case, then on the basis of size factor it would not be expected that any element can replace carbon in FeaC, since according to Schwarzkopf and Kieffer4 the covalent atomic radii of nitrogen, carbon, and boron are 0.71, 0.76, and 0.87A, respectively. Nevertheless, Vogel and Tammann in 1922 indicated that a quasi-binary relation exists between the interstitial compounds FeaC and Fe2B and that the solid solubility of boron in FeaC at approximately 1150°C is 1.4 pct B by weight. Because of the apparent disagreement between theory and experiment, the solid solubility of boron in FeaC has been reinvestigated. In addition, the influence of boron on the saturation magnetic moment (per gram) and Curie temperature of cementite was determined. Experimental Procedure A series of Fe-B-C alloys which varied in boron content from 0 to 5.4 wt pct B were prepared by arc melting a 50-g ingot using carbonyl iron, Ache-son AUC graphite, and Cooper grade A boron for starting materials. The composition of these alloys is listed in Table I and shown graphically in Fig. 1. The samples represented by the solid circles were used for X-ray analysis and Curie temperature measurements; by the squares, samples used for quantitative metallography; and by the triangles, samples used for saturation magnetic moment measurements and Curie temperature measurements. After arc melting and subsequent quenching from 1000°C, so that all phases in the resulting microstructure were brittle, one half of the 50-g ingots were pulverized until a powder was obtained which was less than 100 mesh. These powders were then homogenized in evacuated Vycor capsules at 1000°C for 24 hr and water quenched. Although the homogenized powder had sintered somewhat, it was suitable for saturation magnetic moment and Curie temperature determinations, for which the 60 to 100-mesh fraction of the powder was used. For X-ray analysis the homogenized powder was crushed again until a 300-mesh powder was obtained. After crushing, the powder was mixed with Alundum of approximately the same grit size to prevent sinter-

Jan 1, 1958

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947