Search Documents

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By Charles R. Austin, Carl H. Samans

In an earlier serics of studies on 18-8 stainless steel at 600º, 700º, and 800ºC.l one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manufactured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in. dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0.07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recommended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 75Q°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8-in. dia., air cooling followed the annealing treatment. These treatments permitted two direct comparisons: (1) between the 1150" and 950°C. treatments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950" and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By Carl H. Samans, Charles R. Austin

In an earlier serics of studies on 18-8 stainless steel at 600º, 700º, and 800ºC.l one pretreatment was used throughout; viz., 15 min. in hydrogen at 950°C., followed by an air quench. Several manufacturers of this alloy since have expressed doubt as to the suitability of the temperature employed, recommending instead the more customary Strauss treatment as promising superior results. In this subsequent investigation on the effects of the temperature of pretreatment several interesting points have arisen, which are described in this paper. Previous work on our equipment had shown a marked difference between alloys of "similar chemical composition" that had been manufactured by different companies. Accordingly, one mill-bar length was selected from which to prepare all specimens. It could then be assumed that any marked differences in creep characteristics would be due to effects resulting from variations in the pretreatment of the alloy. The material was furnished by the Allegheny-Ludlum Steel Co. in the form of 5/16-in. dia. rod, finished by air cooling from a mill anneal at 1950°F. (1066°C.). It was analyzed only for the elements shown: carbon, 0.07 per cent; chromium, 18.73; nickel, 9.46; manganese, 0.40. Three pretreating temperatures were chosen, the specimens being held for 15 min. in hydrogen at either: (1) 1150°C., to conform to the recommended Strauss treatment; (2) 950°C., to compare with the results of previous tests; or (3) 75Q°C., to initiate precipitation of carbides in the material before testing. As the test cross sections were only 1/8-in. dia., air cooling followed the annealing treatment. These treatments permitted two direct comparisons: (1) between the 1150" and 950°C. treatments to indicate the effect of grain size when all carbides were probably in solution at the start of the test; and (2) between the 950" and 750°C. treatments to indicate the effect of carbide "nucleation" for similar grain sizes.

Jan 1, 1940

By George V. Smith, Daniel E. Sonon

Various mechanical properties of the Ni-Co-C alloy system were investigated to delineate the strengthening effect of carbon. Carbon concentration, cobalt concentration, vain size, temperature, and strain rate were varied so that thermal activation analysis and the Hall-Petch analysis could be used to evaluate the strengthening effect of carbon. Increasing carbon increased the strength of nickel and a Ni-60 pct Co alloy , with the effect becoming more pronounced at lower temperatures. Yield stress depended linearly on carbon concentration in nickel, but it depended on the square root of carbon concentration in the Ni-60 pct Co alloy. The Hall-Petch slope of nickel increased with carbon concentration; however, that of the Ni-60 pct Co alloy did not. The yielding behavior of these alloys was sensitive to composition, grain size, and temperature. Cobalt eliminated serrations in the flow curve of carbon-containing nickel at 300' and weakened them severely at higher temperatures. Pairs, or clusters, of carbon atoms appear to be responsible for the observed strengthening behavior. FLINN' conducted several experiments with carbon in nickel in an effort to provide information on the strengthening effect of interstitial impurities in solid solution in fcc metals and alloys. Strengthening which increased with decreasing temperature led him to conclude that carbon causes Cottrell locking in nickel. Fleischer2 analyzed Flinn's data and calculated that the strengthening effect of carbon in nickel was smaller by a factor of fifty than the strengthening effect of carbon in a! iron. Fleischer2 termed the magnitude of strengthening of carbon in nickel "gradual" and that of carbon in a! iron "rapid". He attributed "gradual" hardening to hydrostatic strains and localized changes in modulus of elasticity around solute atoms, whereas he attributed "rapid" hardening to tetragonal strains around solute atoms. Sukhovarov et a1.3-7 reported strain aging and serrated plastic flow in nickel, both of which they attributed to the presence of carbon. Serrated plastic flow has been rationalized by a process involving a series of dislocation pinning and multiplication steps.8, This process is more probable when screw dislocations are strongly pinned. Screw dislocations cannot be pinned by pure hydrostatic forces from the symmetrical strains of an interstitial impurity in an fcc lattice, except for small, second-order effects. However, they might be pinned by localized changes in modulus of elasticity around solute atoms,' by the pinning of the edge components of the partial dislocations of an extended screw dislo~ation,'~ or by clustered groups of solute atoms whose net elastic stress field is unsymmetric. The purpose of the present work was to investigate various mechanical properties of the Ni-Co-C a1loy system which are sensitive to pinning effects in order to delineate the specific pinning mechanism of carbon. Carbon concentration, grain size, temperature, and strain rate were varied so that thermal-activation analysis and the Hall-Petch analysis could be used to evaluate the pinning mechanism. Cobalt was added to lower stacking fault energy so that the number and extension of split, screw dislocations would be increased in order to test the possibility of pinning by carbon at extended screw dislocations. EXPERIMENTAL PROCEDURE Nickel and cobalt (both 99.98 pct-. pure) were melted with graphite in stabilized zirconia crucibles and cast at lo-' Torr to form Ni-C and Ni-60 pctCo-C alloys. Two ingots were heated to 1250°C and were forged to 1-in.-sq bars. These bars were machined to 4-in.-round bars, and then swaged cold to 0.144-in. -diam rods. Reductions in area of approximately 75pct were used with intermediate anneals at 900°C for 1 hr. The carbon content of batches of 0.144-in.-diam rods from each ingot was reduced to two levels by annealing 5-in. lengths in palladium-purified, dry hydrogen at 1100°C for 25 and 100 hr. The remaining material from each ingot was annealed at 10"5 Torr for 1 hr at 1100"~. These treatments gave a total of three carbon levels for both the nickel and the Ni-60 pct Co alloy. The 0.144-in.-diam rods were swaged to 70-mil wire, cut into test specimens, and then re crystallized at lom5 Torr in capsules for 1 hr at temperatures ranging from 760" to 1050" ~. The capsules were broken and the specimens were immediately quenched into water. Average grain size was measured using Hilliard's method of circular intercepts." Annealing twin boundary intercepts were counted in addition to grain boundary intercepts to establish an average grain size. Average grain sizes ranged from 5 to 140 p depending on the cobalt concentration and re-crystallization temperature. Tension tests were made in duplicate at various temperatures at a crosshead speed of 8.34 x 10"4 in. per sec with an Instron Universal Testing Machine. Specimens of 1-in. gage length with soldered ball ends were used at atmospheric and cryogenic temperatures. Pinch grips were used on specimens at elevated tem-

Jan 1, 1969

By J. R. Long, E. T. Hayes, R. S. Dean, F. S. Wartman

THE production of titanium in 15-1b. lots and with a purity sufficient to be consolidated into ductile metal, as described in a previous paper,1 has provided adequate material for a study of the : physical properties of titanium and a more thorough examination of its working qualities. Data on the physical properties reported in that paper were obtained on metal fabricated by a fixed procedure, standardized for the purpose of control of the reduction, and are representative only of material fabricated under those conditions. There are many possible variables in the working schedule, which will have significant effects on the properties of the finished material; and since the previous working methods were not necessarily the best, an investigation of the fabrication of titanium by other methods was undertaken. In this work the consolidation of the powder by pressing and sintering was conducted essentially as outlined in the report cited' and all efforts were centered on fabrication methods for those powders and the properties produced by them. Hardness, density, microstructure, and tensile properties were determined at various stages in the working and annealing; and resistivity measurements were made on a few bars and drawn wire. [ ] CONSOLIDATION OF THE POWDER The screen analysis of the available titanium powder is given in Table I. No attempt was made to alter the size distribution from that noted because this powder, although coarse by normal powder-metallurgy standards, produced acceptable compacts suitable for the present work. Because of their large specific surface, finer powders are more contaminated by oxygen and produce harder compacts, which are difficult to work. The powder as produced is soft, compresses in a normal fashion, and exhibits very little tendency to adhere to the die surfaces. Unlike aluminum and magnesium powders, it can be readily pressed without the use of die lubricants. When compacted at so tons per

Jan 1, 1946

By G. D. Just

INTRODUCTION Large scale underground mining involves the bulk handling of fragmented material. The cost and efficiency of the mining systems is there- fore significantly influenced by material flow characteristics. Flow problems may occur in the form of ore pass blockages which interrupt the free flow at extraction openings. The costs of such delays can be readily assessed and compared to the costs incurred in reducing blockages by improved fragmentation or larger ore passes. In practice the problem is more complex than this statement suggests because it is generally un- economic to design for zero ore blockages. Another major flow problem occurs in the form of relative movement of ore and waste as the fragmented material is extracted. This produces waste dilution in the recovered ore and influences total ore recovery. This flow problem is much more complex than the ore block- age phenomena. Many questions concerning the precise flow characteristics remain unanswered because of the variability of size distributions, particle shapes, material properties and the total extraction layout and design. Model studies can provide a visual and quantitative illustration of probable flow characteristics but full scale data collection is necessary to evaluate the precision of such information. The methods and types of data obtained must be carefully selected to recover the maximum volume of useful information for operational control and future design. It is essential that honest precision levels are assigned to the data and any subsequent analyses. Grade control data may give misleading short term information on flow characteristics because of the difficulty in knowing the true grade of the mass of material before extraction commences. However, in the long term control of extraction grades is vital to the profitable operation of the mining system. The most efficient extraction design and operational schedule can only be determined after all of the facts and variables are known. This is usually only possible after the orebody has been completely extracted. However, if design and operational personnel have a full appreciation of the nature and variability of material flow under different conditions the best possible results should be achieved. The most significant features of material flow are out- lined in this paper in order to provide mine planning and mine management personnel with some of the necessary information relating to material flow. Available facts and reliable figures from selected publications are noted in association with unbiased and hopefully accurate opinions of the relevance of the data to mine design and mine system control. Possible future developments and profitable areas for research into material flow problems are also detailed. MATERIAL FLOW AND MINING METHODS The effects of material flow on the design and operation of an integrated underground ore handling system is one factor which is common to most mining methods. Analysis of the system as detailed by Just, 1980, permits the identification of unit process objectives. For example, a typical underground ore handling system as illustrated in Figure 1, involves the following unit operations:- (i) Gravity flow of ore in stope (ii) Ore extraction at base of stope (iii) Ore haulage on the production level (iv) Dumping of ore into ore pass system (v) Gravity flow of ore in the ore pass (vi) Underground crushing of ore (vii) Haulage of crushed ore to shaft (viii) Hoisting of ore to the surface. Average flow rates in each of these unit operations can be misleading due to variability in incremental capacity caused by flow blockages and machine delays. Thus to effectively analyse the probable performance of the system, it is necessary to have a measure of the flow loading and haulage rate variability. Mechanical equipment performance specifications can be used to provide such information for loading, haulage and crushing; however, in the case of the gravity flow of material field measurements are required to relate the probability of "hang-ups" to the degree of fragmentation. Factors affecting the frequency of flow stoppages are, size, distribution and cohesiveness of broken material and the geometry and size of the flow channel. Ore pass channel design is relatively simple since regular cross-sectional shapes are used

Jan 1, 1981

By H. N. Eavenson

EaRly in 1917, the United States Coal & Coke Co. secured options on several tracts in Harlan County, Ky., aggregating about 19,000 acres in area, and after careful prospecting by outcrop openings and diamond drilling, completed the purchase late in July of that year. This property is situated in the eastern end of Harlan County, south of the Poor Fork of Cumberland River, and extending across Big Black Mountain to the Clover Fork of Cumberland River, a distance of about 7 mi. (11.3 kg.). It extends from the Kentucky-Virginia line westward for about 6 mi. Looney Creek, which empties into Poor Fork, crosses the property for about 4 mi. (6.4 kg.), and as several of the seams within the property outcrop along this stream, it afforded an easy, and the logical, place for development. The property is on the northern side of the geological trough formed by the uplifting of Stone Mountain, on the southern, and Pine Mountain, on the northern side; the northern boundary along Poor Fork is practically at the base of Pine Mountain. This area has been described in various geological reports. The main seam on this property is the one known variously as the "C," Benham, Keokee, Taggart, and Roda; it is also called, by the Kentucky Geological Survey, the Kellioka seam of the western portion of Harlan County. This seam averages, in this property, about 5 ft. (1.5 m.) in thickness, although local rolls reduce this thickness considerably over small areas, and at the extreme western end of the property the seam splits. It is usually clean, although occasionally a small parting occurs within a few inches of the bottom of the seam; it is one of the best coking and gas coals in the United States. The average analysis of this coal is given in Table 1.

Jan 1, 1922

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By B. L. Averbach, M. Cohen

THE PROBLEM MANY hardened steels contain significant quantities of retained austenite even in cases where the carbon and alloy contents are low. In fact austenite has been detected in plain carbon steels containing as little as 0.50 pct carbon.1 Although the austenite may not be visible metallographically it causes definite dilatometric and magnetic effects during subsequent tempering or subatmospheric cooling.1,2,3 Therefore if the reactions which hardened steels undergo during later treatment are to be understood in quantitative fashion it is most essential to have some kind of absolute analysis for the austenite content in hardened steels. Once this analysis has been made, the austenite transformations can be followed precisely by observing such sensitive phenomena as changes in length or in magnetization but the latter techniques can only determine differences in the amount of retained austenite and usually an independent method must be found to put these differences on an absolute basis. In certain instances the microscope can be used advantageously to determine the percentage of retained austenite. The quenched sample is tempered to "darken" the martensite with minimum decomposition of the coexisting austenite, and then is polished and etched in the usual fashion. If the austenite is clearly distinguishable from the tempered martensite and other possible constituents its volume percentage can be measured quantitatively by point counting or lineal analysis.4 Such microscopic methods, however, depend on the etch being sufficiently discriminatory. In fairly coarse structures, if the austenite content is greater than 10-15 pct, there is probably little smearing of the etch, and point counting or lineal analysis seems to be quite accurate. On the other hand if the structure is difficult to resolve, as in commercially treated fine-grained steels which contain less than 10-15 pct retained austenite, the latter may be completely obliterated by the dark etching martensite or it may appear disproportionately low as the interfaces between the two constituents become difficult to distinguish. Another disadvantage of the metallographic method is the need for "darkening" the martensite and hence the determination cannot be applied to as-hardened steels. The required tempering may spoil the structure for other tests or may even remove a small part of the austenite which is being sought. X ray methods hold more promise for covering the range under 15 pct retained austenite. Although austenite and martensite in the hardened steel may be chemically identical, their crystal structures and lattice parameters differ, and the intensity of an austenite diffraction line is some continuous function of the percentage of re-

Jan 1, 1948

By W. V. Youdelis, W. H. Bear, G. Cochrane

HERETOFORE, there has been very little study of the effects of various metallurgical factors on the behavior of thermoelectric materials, the need for which is evident if optimum processing and design of thermoelectric devices is to be realized. Accordingly, we have undertaken such an investigation on the thermoelectric materials bismuth and Bi-Sb alloy and in this paper present some preliminary results which merit consideration, in particular the relatively high thermoelectric power and figure of merit values obtained for the Bi-12Sb (at. pct) alloy powder compacts. The thermoelectric parameters for ingot and powder compact specimens are determined and the results are compared with published data for single crystals. Preparation of Materials. The bismuth and antimony used in this investigation are six nines pure. Melting and casting of the ingots was carried out in air for expediency, since most oxidation unavoidably occurs during the preparation of the powder by filing of the ingots. Chill cast ingots of pure bismuth were prepared by pouring the melt into split copper chill molds, and unidirectionally solidified ingots of bismuth and Bi-Sb alloy were obtained by slow directional cooling in pyrex tubes. All melts remained bright during melting and casting, indicating minimum oxidation. Powder for the powder compact samples was obtained by filing the ingots with a fine and coarse file to give a variation in the particle size of the compacts. The particles in the fine powder compacts varied in size from approximately 28 pct less than

Jan 1, 1970

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,&apos; appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.&apos; For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,&apos; polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By H. W. Graham

[ ] Even though we have a small audience, I am sure there are some here who are interested in sponge iron. It is a large subject, with a lot of economic interest, and one that will continue to grow in importance as the years go by and as the conditions that urge action in that direction increase. The authors have chosen to deal in this paper with one particular narrow phase of a long program of work by the Bureau of Mines. Before asking for any general discussion, I would myself like to ask Mr. Buehl if he would tell us just a little bit about the mechanism of discharge and the form in which the material was discharged; that is, when dolomite is added, what happens to the dolomite? R. C. Buehl (author&apos;s reply)-You are interested in the equipment that was used? H. W. GRAHAM-No, just the product. R. C. Buehl-The product was in granular form, of a shape very similar to that of the ore used. Using minus 10-mesh ore, the product is essentially minus 10-mesh, mixed with the coal and dolomite. It is then passed through a belt type of magnetic separator, which picks up the magnetic iron and allows the dolomite and coal to fall off. If the coal is sufficiently valuable, it can be separated from the dolomite and, provided the coal has a sufficiently low ash content, it can be reused. For instance, if a low-ash reducing agent like petroleum coke is used, it can be reused until all the carbon is consumed. H. W. Graham-That clears the point for me. I was not quite sure whether the experi-

Jan 1, 1947

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.&apos; It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12&apos;13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By C Macquarie, Maurice Cook

Normally the grain size of cold-rolled and annealed copper sheet is of the order of 0.02 to 0.06 mm., and 0.1 mm., for example, would, for many purposes, be regarded as undesirably large. The occurrence of very large grain sizes in a few isolated cases of copper sheet led the authors to inquire into the causes giving rise to such unusual results. During the course of this work a very large number of experiments have been carried out to determine the effect of varying the conditions of the final and penultimate rolling and annealing operations, as well as of earlier rolling and annealing treatments. A correspondingly large number of observations have been made, but within the space of one paper it is possible only to outline relatively briefly what appear to be the more important of these experiments and observations. The presentation of the results does not follow chronologically the order in which the experiments were carried out and they have been rearranged for the sake of simplicity. In recent years a considerable amount of work has been done in connection with the recrystallization and grain growth in metals arid alloy. that take place on annealing, and a number of generalizations have beell reached. It is known that the crystal size in wrought material in the annealed condition depends on a number of factors, including the time and temperature of the annealing operations and the nature and amount of cold-work to which the material has been subjected. Results. however that are not covered by these generalizations can be obtained, which, in some instances, may even appear to be contradictory to them. Xccortling to these generalizations gradual changes in grain size are effected by progressive variation of the factors involved in annealing or cold-working. The work recorded in the present paper, however, relates to the development of grain sizes which are far beyond those normally encountered in ordinary annealing operations and far in excess of grain sizes which,

Jan 1, 1939

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith&apos; indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.&apos;&apos; Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By H. M. St. John

THE melting department is the heart of the foundry. From it clean metal flows to the molding floor, in the right quantity, at the right time and at a sufficiently low cost-or, if not, the foundry fails to thrive. Since it is our purpose here to discuss present-day melting practice in the foundry, it may be well at the start to emphasize the wide differences in foundries and the conditions under which they must operate in order to reach the goal stated in the first paragraph. In every foundry, large or small, jobbing or captive, the same factors must be dealt with but they are of varying consequence and must be dealt with in varying ways in different foundries. Particularly in the nonferrous industry, there is so wide a variation in the composition of alloys used and in the character of castings made that no one type of furnace, nor any one method of operation, can be expected to produce the best results at all times. The present discussion will not attempt to include all nonferrous metals. It is intended to cover only the copper-base alloys in which copper is the dominant element, most of which are commonly known as brass or bronze. The discussion is further limited to the melting of these copper-base alloys for use in sand-casting foundries. Die-casting plants, the brass-rolling mills and certain other metal industries have melting problems peculiar to those industries, which will not be considered here. The following considerations are elemental in all foundries and are listed in what is believed to be the relative order of their present-day importance: I. The melting department must meet the foundry&apos;s requirement for dean, fluid metal, of specified composition and purity, at a temperature suitable for the work the foundry has in hand. This is the prime consideration in any foundry, at any time, anywhere. 2. Working conditions surrounding the melting furnaces and attending their use must be good. 3. The cost of molten metal at the mold must be as low as possible. 4. The operating characteristics of the furnaces must be sufficiently flexible, to meet normal variations in foundry requirements. 5. The operation and maintenance of the melting equipment must not require more skill and experience than is available in the particular foundry in question. METAL QUALITY It is not a function of the melting furnace to refine or improve the quality of the metal but simply to melt it without impairing its quality. Good practice requires, therefore, that care must be taken to supply the melting department with metal of inherently good quality, assured by specification or otherwise, having all the properties necessary to produce the castings desired. An alloy contains a number of primary elements, which must be present in definite proportions if the castings made from it are to have the desired properties. If the castings are made to a customer&apos;s specification, this will state the range within which these principal elements (for example, copper, tin, lead and zinc) are permitted to vary.

Jan 1, 1946

By N. H. Jensen, B. L. Sackett, Carlos Bardwell, Simon Jacobson

Lead smelting has been an important industry in Utah for many years. The first lead smelting was done, over 60 years ago, at the Rollins mine in Beaver County, by burning heaps consisting of alternate layers of wood and high-grade carbonate ore. The lead thus obtained was molded into bullets. With the development of the mines, the problem of cheaper handling of the ore became important. The only outlet for this ore was Swansea or the Atlantic Coast but to ship to either cost $150 per ton or more for treatment and handling. From 1864 to 1871, experimenting was done with blast, Scotch hearth, and reverberatory furnaces, with the blast furnace surviving as the standard plant. The first crude furnaces were circular or hexagonal in shape, and were made of adobe and stone, which quickly burned out. They were small, about 21/2 ft. in diameter, and smelted from 3 to 10 tons in 24 hr. The metal had to be tapped from the bottom of the crucible, necessitating a shut down of the furnace during this process. This procedure caused salamanders to form around the tap hole when the furnace was started again, which frequently resulted in freezing. The campaign lasted until a tap of bullion was made. The first successful plant of the crude stone type was operated in 1870. From 1870 to 1872, there was a smelter building craze in the state. During that period, about 20 furnaces were built, chiefly near the mines, and their operation was limited and sporadic. The work was then placed in the hands of trained metallurgists, who standardized on the rectangular form of furnace. In 1871, Daggett, at the Winnamuck mine in Bingham, installed water-jackets around the smelting zone of the furnaces. These furnaces were circular; the diameter at the tuyere line was 3 ft. 6 in. and at the charge floor 5 ft. 3 in. The height from tuyere line to charge floor was 14 ft., height of tuyere line above top of crucible was 3 ft. 8 in. Furnace capacity was about 14 tons per day, with a campaign of about 16 days. Cost of smelting was about $44 per ton. The ores making the

Jan 1, 1926

By W. N. Poundstone

The mining and ventilating system used in development work in the Pittsburgh Seam in northern West Virginia is discussed. The seam conditions and the nature of the accompanying methane gas are described. The type of equipment and the mining cycle will be discussed, showing how they are well suited for very gaseous development work. Face ventilation in development work is possibly the fastest growing problem of the industry. The coal mines of the future will be faced with the prospect of mining from under increasing depths of cover. Consequently, larger and larger amounts of methane gas probably will be found. The Pittsburgh Seam, in northern West Virginia, is an example of an area already faced with this problem. At the present time, most of the development work being done in this seam lies beneath 500 to 1200 ft of cover. The Pittsburgh Seam in this area has always been very gassy—even near the outcrop—and the recent development work has been accompanied with extremely large volumes of gas. In many cases, a single development section has liberated in excess of 1,000,000 cfm in 24 hr. This problem of heavy gas liberation was the chief concern, several years ago, when continuous mining equipment was first considered at Christopher Coal Co. All of us were apprehensive about the liberation that would accompany rapid extraction in a single working place. However, the experience during the past few years has shown that this ability to mine only one place at a time, is actually the key to working this type of coal. With all of the mining or advancement concentrated in one place, the ventilation can also be concentrated. By this it is meant that continuous mining permits the active working place to be ventilated with a maximum amount of fresh air, taken directly from the intake source without first passing another working place. Continuous mining (and a good ventilating system) also permits a much greater concentration of attention or vigilance to the actual working place. There are two things that are very important to the mining of coal having high rates of liberation. First, adequate volumes of air are necessary. Second, and perhaps more important, a mining and ventilating system must be used that will provide an uninterrupted flow of air to every portion of the working section. Liberations of this magnitude take only a few seconds of interruption for a dangerous accumulation of gas to occur. With adequate volumes of air available, the ability to concentrate ventilation more than offsets the concentration of gas emission that is inherent with continuous mining. The mining system used with continuous mining equipment at Humphrey Mine is similar to the system used at many mines in the area for development work. This system is designed to favor ventilation, realizing that other efficiencies are meaningless if the equipment must stop because of ventilation difficulties. This plan is especially well suited to minimizing ventilation interruptions. Basically, the overall plan of mining is to develop headings into virgin coal and encircle or block out large areas. These blocks are generally at least 2000 ft sq. The purpose of this blocking out is to bleed gas from the area before pillaring. Experience has shown this method to be quite effective, even in the most gassy areas. The gas in this field seems to migrate or flow readily from the solid coal into the outside return headings of the development work. The numerous clay veins and slips that are found in the area are extremely good avenues for gas flow. A block of coal, surrounded with development headings, usually bleeds off readily; and since it is cut off from the virgin coal, it is not subject to gas migration, through the seam, from this source. However, the outside return of the encircling development work, adjacent to the virgin coal, may liberate gas for years. This liberation from the outside ribs in the virgin coal is the reason split ventilation is used in development work. If split ventilation were not used, there would, in many cases, be a serious build-up of gas in the intake before it could reach the working face. Fig. 1 shows a typical development section having seven headings. The two outside places on each side are returns, and the three center headings serve as intakes. This section is equipped with a ripper-type continuous mining machine. An off-track loading machine is used to load from a surge pile on the

Jan 1, 1961

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman&apos; reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser&apos; reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,&apos; values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,&apos; on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.&apos; When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959