Search Documents

By M. A. Selim, W. H. Somerton

Thermal expansions and heats of reaction of three typical sandstones were measured in the temperature range of 25°to 1,000°C. The significance of these data in subsurface heat-transfer calculations is discussed. Linear thermal expansions were measured both parallel and perpendicular to the bedding planes. Volume expansions are reported as the perpendicular expansion plus two times the parallel expansion. Expansion behavior of the sandstones was found to be controlled by the expansion characteristics of the quartz content. Differential expansion of the quartz grains and other minerals included in the sandstones caused permanent deformation of the heated samples after they were cooled to room temperature. Structural damage resulting from heating is probably an important cause of the reduction of thermal conductivity of heated samples. Measurements of heats of reaction were based on the known heat required for a- quartz inversion. Thermal reactions, which probably include deby-droxylation of clay minerals and decomposition of carbonate minerals contained within the samples, were found to require more than one-fourth of the amount of heat necessary to raise the temperature of the rock alone. In shales and limestones, the reaction heat could be substantially greater than that required from specific heat considerations alone. INTRODUCTION In earlier work, l-3 methods of measuring thermal properties were developed and thermal data for several sedimentary-rock types were reported. Data included thermal conductivity, specific heat and thermal diffusivity. In addition, calculations of heat transfer in subsurface formations may require data on the thermal-expansion characteristics of rock and the heats of reaction of mineral constituents. Thermal expansion of rocks is relatively small in magnitucle and, from the standpoint of change in bulk density, has only minor effects on heat-transfer cliaracteristics. Thermal-expansion behavior, however, may have significant effects on the structure of rocks. Differential expansion of different minerals and along different crystal-lographic axes may result in structural damage which could effectively reduce the thermal conductivity of the rock. Many mineral constituents of sedimentary rocks undergo phase or related changes when heated to sufficiently high temperatures. Although some of these reactions (such as the a-ß quartz inversion) are reversible and the heat absorbed is returned to the system upon cooling, many of the major reactions are irreversible. Through certain temperature ranges, the additional heat energy required to complete the reactions may be nearly as great as that necessary to raise the temperature of the rock in the absence of thermal reactions. If the heat requirements for these reactions are not considered, serious errors in heat-transfer calculations may result. Thermal-tzxpansion and thermal-reaction data have been obtained for three typical sandstones. Methods of measurement and results obtained are reported and discussed in the following. THERMAL EXPANSION OF SANDSTONES The linear expansions of three outcrop sandstones (Bandera, Berea and Boise) have been measured in the temptbratue range of 25° to 1,000° C. Expansion measurements were made in the directions parallel and perpendicular to the bedding. The differential expansion apparatus used is that described by Mitoff and Pask.4 The test sample is heated in an electric furnace with a temperature rise of 6°C/minute. The lengthening of the samples upon heating is compared with the small and known expansion of a fused silica rod. The change in length is transmitted to an X-Y recorder by means of a Statham transducer. A maximum error of ± 1.5 per cent has been obtained with this apparatus

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By H. I. Aaronson, C. Laird

Cold rolling by 50 pct a A1-4 pct Cu alloy containing many 0' plates has been found to accelerate markedly the transformation of 8' to 0 upon further aging. Although the basic mechanism of this transformation remains unchanged by plastic deformation, the nuclea-tion kinetics of 8 become appreciably more rapid and also less dependent upon temperature. Particularly at lower aging temperatures, rounded idiomorphs replace several faceted rnorphologfes. The rates of growth of 9 idiomorphs in deformed specimens aged at 300°C are appreciably more rapid than simple volume diffusion control allows. This observation is shown to be explained by an excess vacancy, rather than by a dislocation Piping mechanism of growth. ThE rather complex phenomenology of the 8' —8 transformation in Al-Cu alloys has been recently elucidated in considerable detail by means of transmission electron microscopy.'-4 This technique was also employed in the present investigation in order to examine the effects of plastic deformation upon the transformation of 8' to 8. The mechanism of the transformation in undeformed Al-Cu alloys has been established as the following sequence of events.1"4 The first step is the nucleation of 9 at (Y:8' boundaries. Nucleation of a 0 crystal takes place, however, at only a very small proportion of the 8' plates present. Each 0 crystal simultaneously consumes the host 8' plate and the a! in the immediate vicinity, with growth into a being the rate-controlling process. The remaining 8' plates are then dissolved as they fall under the concentration shadow of the growing 8 crystals. The evidence on the effects of plastic deformation upon these processes is intriguing, but much less detailed. The careful X-ray studies of Graf and Guinier have shown that the aging times required to form detectable amounts of 8' and 8 are reduced by prior cold working. Thomas and Nutting confirmed these results by replication electron microscopy. Nile-shwar,* on the other hand, reported that creep deformation decreases the rate of formation of 0. While this difference may have been caused by the use of concurrent rather than successive deformation and ag- ing, the X-ray technique which he used was able to monitor only the 0 phase. It is thus possible that the times needed to form 8' were increased moreg than the kinetics of 8' — 8 transformation were accelerated. At 90 pct deformation by cold rolling, Graf and Guinier found that the usual 0' —0 8 sequence is reversed: 0 forms first. von Heimendahl 10 confirmed this result with transmission electron microscopy. Pollard and Nutting, 11 and more recently Driver and Barrand, 9 having used the same technique, report that 9 also forms first during creep deformation. In the present study, the maximum amount of deformation was limited to 50 pct reduction by cold rolling in order to insure that 8 formed principally by the decomposition of . I) EXPERIMENTAL PROCEDURES This investigation was conducted on an Al- 3.93 pct Cu alloy, prepared as previously described. 4 Morphological and crystallographic effects of plastic deformation were studied in specimens annealed 6 hr at 548°C, quenched, and then aged for either 3 or 8 hr at 250°C to form large numbers of 0' plates. After cold rolling to a 50 pct reduction in thickness, the

Jan 1, 1969

By N. S. Bornstein, M. A. DeCrescente

ThE nickel and cobalt base superalloys employed in gas turbine engines under some conditions' oxidize at an accelerated rate when exposed at elevated temperatures to atmospheres containing minor quantities of sea salt. It is generally agreed by investigators in the field that the major steps comprising this phenomena of accelerated oxidation, also called hot corrosion or more commonly, sulfidation, are a) a slag composed primarily of Na2S04 is formed on turbine components, b) the protective oxide scale is rendered ineffectual, c) the slag reacts with. the substrate to form metal sulfides, and d) the substrate is rapidly oxidized. Sodium sulfate, a minor constituent of sea salt, is formed within the gas turbine engine from the reactions between NaC1, the major constituent of sea salt, and the oxides of sulfur.' Depending upon concentration, engine compression ratio, and temperature, the Na2S04 will be present in the gaseous or condensed state. It has been determined that in order for sulfi-dation to occur the Na2S04 must be present in the condensed state.' Although a number of sulfidation mechanisms have been postulated, there is no consistent explanation of oxide scale breakdown and subsequent catastrophic oxidation. Some investigators believe that after oxide scale breakdown, the Na2SO4 reacts with the substrate to form lower-valent sulfur compounds. The accelerated rate of oxidation is due to oxidation of a nickel-sulfide phase." Other investigators believe that sulfur from the fused salt reacts with chromium in the alloy to form chromium-rich sulfides; thereby depleting the alloy of an element which imparts oxidation resistance.3,4 This publication will demonstrate that the accelerated rate of oxidation associated with sul-fidation is due to interactions between Na20, a con-stituent of NazSO.,, ancl the substrate. The aim of this study was to separate and determine the effect of compounds of sulfur and sodium on the oxidation kinetics of various nickel-base superalloys, in order to elucidate the sulfidation mechanism. The work reported herein is sponsored in part by the Naval Ship and Development Center-Investigation of EXPERIMENTAL PROCEDURE The nickel base alloys B-1900, U-700, and Waspaloy were chosen for this study. The nominal compositions are presented in Table I. The specimens, approximately 1 in. by 1 in. by 0.060 in. received in the "as cast" condition were polished with 600 grit emery, washed, and rinsed with acetone immediately prior to oxidation experiments. Sulfida-tion attack was duplicated in the laboratory by apply-ing a saturated aqueous solution of Na2S04 onto the al loy substrate and subsequently exposing the specimens in oxygen at elevated temperature. The method of Na2S04 application is described elsewhere in detail.6 In another set of experiments the affected substrate microstructure associated with sulfidation was reproduced free of the normal oxide scale, by reacting and diffusing elemental sulfur into the alloy. The experimental procedure is also described elsewhere in detail. All oxidation studies were performed using an Ainsworth thermobalance type RV-AU-1, which is readable to 0.01 mg and is reproducible to ±0.03 mg. The specimens, introduced into a heated furnace, were exposed in the temperature range 800" to 1000°C

Jan 1, 1970

By E. S. Lenker, H. J. Van Hook

A complete swies of solid solutions has been found between the compounds InAs and GaAs Below the solidus. The melting relations determined by differential thermal and static quenching technzques, indicate that the liquidus and solidus are of the simple ascendant type. No evidence of unmixing of the homogeneous solid solutions was observed at sub-solidus temperatures. A quenching method for locnting the solidus, using X-ray diffraction techniques, is described in some detail. THE semi-conducting properties of compounds formed by various combinations of the less familiar intermetallic elements have created an increasing interest in the phase relations in systems involving these elements. The complete phase diagram of such a system, containing a compound of special interest, will often provide information as to the most favorable conditions for preparing large crystals from a melt, as well as specifying the temperature stability of the crystalline phase or phases produced. In view of the current importance of gallium arsenide in semiconductor research and of the structural similarities of indium arsenide, it was thought that the complete phase relations of the system InAs-GaAs should be investigated. Previous work on the system Ga-As by Koster and homa' and on In-As by Liu and peretti2 has shown that GaAs and InAs are the only compounds formed, having melting points of 1238° and 942°C, respectively. In a survey of various systems of elements from groups IIIb and Vb, spengler3 also re- Mines Ltd., for his continuing encouragement and for permission to publish the results of this work. ports complete miscibility of gallium, indium, and arsenic in the liquid state. In a partial investigation of the InAs-GaAs system, Woolley and smith4 found extensive solid solution throughout the alloy range. Their subsolidus work, however, was inconclusive at temperatures below 900" and they did not determine the liquidus relationships of the system. PRESENT INVESTIGATION The starting materials used were high-purity gallium, indium, and arsenic. The method of preparation of the compounds follows that devised by M. Shafer and is described in detail in a paper by Shafer and eiser.' The end-member compounds, GaAs and InAs, were first prepared by reaction of the elements in the desired proportions in evacuated silica glass vials. The vials were rotated in a furnace as the temperature was slowly raised to insure rapid and complete reaction at low temperatures. Thereafter the starting materials, GaAs and InAs, were melted by heating the sealed vials to 1300" and 1000°C, respectively; the vials in this case were filled as completely as possible to keep the vapor space small and thereby minimize the loss of arsenic to the vapor phase. Ten binary mixtures of these compounds were then prepared by reaction of the powdered material in the solid state just below solidus temperatures. At 900C preparations containing 3, 5, 8, 10, 25, 35, 50, and 75 mol pct GaAs were found to be single homogeneous phases, indicating a complete series of solid solutions between GaAs and InAs. Moreover, it was discovered that the homogeneity of any crystalline binary preparation could be very accurately checked by X-ray diffraction because of the large differences in unit cell dimensions of the end membe5s. The cubic lattice constant ofor GaAs is a = 5.652A and that of InAs is a = 6.061A

Jan 1, 1963

By David A. Thomas, David N. French

The lrnrdness of WC crystals has been measured with the Knoop indenter at loads of 100 and 500 g on the (0001) and (1070) planes. The hardness as tneasitred on the basal plane is 2400 kg per sq mm and shows little anisotropy. The hardness on the prism plane, however, shows a marked orientation dependence, with a low value of 1000 kg -per sq mm when the long axis of the Knoop indenter is oriented parallel to the c axis and a high value of 2400 kg per sq mm when the indenter is perpendicular to the c axis. Slip lines (Ire observed surrounding the microhardness indentations and they show slip on (1010) planes, probably in [0001] and (1120) directions. This slip behavior can be explained by the crystal structure of TVC, which is simple hexagonal with a c/a ralio of 0.976. The hardness anisotropy call be explained by [0001]{1010} and (1130) {10l0] slii) and the resolved shear-stress analysis of Daniels and Dunn. HARDNESS anisotropy is a well-known phenomenon and has been reported for many metals, with both cubic and hexagonal structure.1-6 For hexagonal tungsten carbide, WC, a wide range of hardness values is reported in the literature. For example, Schwarzkopf and Kieffer7 give a hardness of 2400 kg per sq mm and report a value of 2500 kg per sq mm by Hinnüber. Foster and coworkerss give the average Knoop microhardness as 1307 kg per sq mm with a maximum value of 2105 kg per sq mm. Although these values and the structure of WC suggest the likelihood of hardness anisotropy, no such measurements have been made. We first detected a large apparent hardness anisotropy in WC crystals about 75 p large, in over-sintered cemented tungsten carbide. Prominent slip lines also occurred around many indentations. This report presents further observations and interpretations of hardness anisotropy and slip in WC crystals obtained from Kennametal, Inc. Both Knoop and diamond pyramid indenters were used on a Wilson microhardness tester with loads of 100 and 500 g. EXPERIMENTAL RESULTS The carbide crystals tended to be triangular plates parallel to the (0001) basal plane of the hexagonal structure. The side faces were parallel to the ( 1010) prism planes. Specimens were mounted approximately parallel to these two types of faces and metallographically polished. Laue back-reflection X-ray patterns were used to orient the specimens, which werethen ground to within ±1 deg of the (0001) and (1010) planes. The Knoop hardness values measured on the basal plane are plotted in Fig. 1. There is only a small anisotropy, with a hardness range of 2240 to 2510 kg per sq mm. The additional points at angles from 52.5 to 67.5 deg confirm the sharp minimum hardness at 60-deg intervals, consistent with the sixfold hexagonal symmetry. The average hardness of all values obtained on the basal plane is 2400 kg per sq mm. While the basal plane shows only slight anisotropy, the (1010) plane exhibits marked hardness anisotropy, from 1000 to 2400 kg per sq mm. Fig. 2 shows the hardness as a function of the angle between the long axis of the indenter and the hexagonal c axis, the [0001] direction. The minimum and maximum occur when the indenter is oriented parallel and perpendicular to the [0001] direction, respectively. The anisotropy of the prism plane is contrary to that reported for hexagonal zinc and hard- However, the basal-plane anisotropy is similar to these two metals.1'2 To check the accuracy and reproducibility of the measurements, a series of fifteen impressions was made at 100-g load in the same orientation in the same area of the specimen surface. The average for all was 2040 kg per sq mm, with a range of 1950 to 2130 kg per sq mm, giving an accuracy of about ± 5 pct. Thus the slight anisotropy on the basal plane is almost within experimental error. Fig. 3 shows slip lines around the Knoop indentations on the basal plane. The slip traces are in directions of the type (1130). The presence of slip steps on the basal plane indicates that the slip direction lies out of the (0001) plane. Because WC has a c/a ratio of 0.976,' the shortest slip vector is [0001], which suggests slip systems of the type [0001] (1010). Fig. 4 shows slip lines around the Knoop intentations on the (1010) plane. These slip lines are inconsistent with [0001] slip but can be

Jan 1, 1965

By J. B. Hiskey, G. Ramadorai

This paper presents the kinetics of leaching pure wulfenite (PbMoO,) with sodium sulfide solutions. Wulfenite dissolves in the presence of sulfide ion according to the following reaction: PbMoO , + S= PbS + MOO;. Synthetic galena is formed and molybdenum is released to solution as molybdate ion. The reaction follows the shrinking core model and the leaching mechanism involves mixed kinetics where both diffusion and chemical reaction are rate controlling. Molybdenum extraction is explained in terms of temperature, particle size, and sodium sulfide concentration.

Jan 1, 1977

Dr. James Douglas, who is memorialized on another page of this Bulletin, who held a place in the affections and regard of Institute members second to that of no other living roan, left in his will the sum of $100,000 for the maintenance of the Library of the American Institute of Mining Engineers. This is in addition to the $100,000 which Dr. Douglas gave during his lifetime. We believe that it is Dr. Douglas' wish that the library, the great means by which the benefits of Institute membership may be extended to those distant from headquarters, should be maintained by the Institute at the highest possible level of efficiency and serviceability.

Jan 9, 1918

J. E. JOHNSON, JR., New York.-It seems to me that it ought to be somebody's job to tie these notch tests with the reversed-stress tests, because the thing that causes failures in structures, in a great majority of cases, is where the material is stressed repeatedly up somewhere near the elastic limit, and the repetition of that stress seems to bring about what I suppose you may call a growth of crystals and that eventually develops into a break. It seems to me that it would be of the greatest value if there could be a coordination of the results of a shock test of some kind with the reversed-stress test, so that we could be sure that a material that had shock-test resistance would have reversed-stress resistance. H. F. MOORE,* Urbana, Ill.-The question raised by the speaker concerning the correlation of results from impact tests of notched bars with the results of repeated-stress tests is a very complicated one. Impact on a specimen sends energy into the specimen, and if the specimen absorbs this energy without fracturing there must be developed both stress and elongation. A notch in the specimen allows but little elongation to take place before rupture, and develops the ductility of the

Jan 5, 1919

By W. L. Phillips

Nickel alloys containing approximately 0.5, 2.0, and 6.0 at. pct of Os, Pd, Ru, and Rh were Prepared by vacuum melting. Tension tests were carried out at 25°, 500°, 800°, and 1000°C; stress-rupture tests were carried out at 650° and 800°C. The room- and elevated-temperature tensile strength, as well as the stress-rupture life, increased for the same atomic percent in the order palladium, rhodium, ruthenium, osmium. The ductility decreased with increasing concentration or temperature for a given concentration. The results are discussed in terms of solid-solution theory. BOTH solid-solution strengthening and weakening have been observed in alloys. The simple rules which have been suggested to explain alloy strengthening are subject to several exceptions and deviations based on atom size and valency effects. The purpose of the present investigation was to extend the knowledge of the effect of solid-solution alloying on the mechanical properties of several Ni-Pt group metal alloys at room and elevated temperatures. The platinum group metals, osmium, ruthenium, rhodium, and palladium were chosen as the solute elements because of their different valencies and atom sizes. Nickel was chosen as the base material because of the large amount of previous literature available on nickel alloys. EXPERIMENTAL PROCEDURE Grade A Carbonyl nickel powder having the following composition: C, 0.07 pct; Fe, 0.013 pct; Mn, 0.0005 pct; Si, 0.016 pct; Mg, 0.0003 pct; S, 0.003 pct, was purchased from the International Nickel Co. The platinum-group metal powders were purchased from A. D. Mackay Co. The powders were weighed, cone-blended for 4 hr, and vacuum-melted into 1-in.-diam billets, approximately 2 in. long. The ingots were homogenized for 5 hr at 1800°F before being extruded into 1/4-in. rods at 2100°F. The alloy compositions are shown in Table I. Typical impurity values were not significantly different than that of the as-received nickel. All alloys were single phase. The lattice parameter of each alloy after the heat treatment described below is also included in Table I. Each alloy was annealed at 2200°F for 1 hr and air-quenched to comparable grain sizes (ASTM G.S. No. 4-5). The rods were then machined into test samples 0.160-in. diam and 0.750-in. gage length. Tension testing was carried out in an In-stron tension-testing machine at a strain rate of 0.02 in. per in. per min. An extensometer was used to determine the room-temperature yield stress. Stress-rupture testing was carried out in an Arc Weld stress-rupture unit. All testing was performed in air. EXPERIMENTAL RESULTS A) Room-Temperature Mechanical Properties. The 0.2 pct yield stress, ultimate tensile strength, and elongation for all alloys tested at room temperature are plotted as a function of atomic percent solute element in Fig. 1. The ultimate tensile strength for the same atomic percent increases in the order palladium, rhodium, ruthenium, osmium. The yield strength at low concentrations, -0.5 at. pct, increases in the order osmium, palladium, ruthenium, rhodium. At higher concentrations, 3.0 and 10.0 pct, the yield strength increases in the same order as the tensile strength. Both yield strength and tensile strength increase rapidly ini-

Jan 1, 1964

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By B. H. Kear, H. G. F. Wilsdorf

After a few percent strain, dislocations in disordered Cu3Au are arranged in groups in ulell-defined slip planes, which contrasts with the more or less random distribution of dislocations in the corresponding ordered alloy. Unusually long and straigkt dislocation segments observed in the ordered alloy are interpreted in terms of cross slip of screw dislocations from their slip planes into cube planes. It is proposed that cross slip, and also dislocation reactions of the Lomer type, play an important role in work hardening of the ordered alloy. ACCORDING to to dislocations in the disordered lattice are only partial dislocations in the corresponding super lattice, so that in the super-lattice dislocations must occur as pairs, with each pair connected by a ribbon of antiphase boundary. Recently, striking confirmation of the theory was obtained by Marcinkowski, Brown, and Fisher3j4 in a study of dislocation configurations in thin foils of the Cu3Au alloy by transmission electron microscopy. In the present investigation, the observations made by these workers have largely been confirmed. Moreover, it has been found that dislocations in the plastically deformed ordered alloys are often unusually long and straight. This paper is mainly concerned with these new observations. A tentative explanation is offered in terms of cross slip of dislocations in the ordered alloys. PREPARATION OF SPECIMENS An alloy close to the stoichiometric composition Cu3Au was prepared by melting together high-purity copper and gold (99.995 pct) under vacuum in a graphite mold. The resulting ingot was rolled down and cut into strips 1 1/2 by 1/8 by 0.005 in. in thickness. All strips were annealed at 900°C for 3 hr and cooled to 500'~. A few of the strips were quenched from ~OO'C, while the remainder were slowly cooled in the temperature range 400" to 150°C at intervals of a few degrees every 24 hr to produce a high degree of order. After this annealing treatment the average grain size of the material was about 0.1 mm. Material in different states of order was obtained by reannealing fully ordered material at temperatures below the critical temperature: followed by quenching. The equilibrium degree of order attained at a particular reannealing temperature was obtained from the paper by Keating and warren.' A simple hand-operated tensile jig was used to give the strips the required amounts of plastic strain. Following straining, a number of specimens were cut from each strip by means of an electrolytic cutting device.= Finally, each specimen was thinned electrolytically using the polishing procedure described by Bakish and Robertson,7 and these thin sections were examined in the Philips EM-100B electron microscope operating at 100 kv. EXPERIMENTAL OBSERVATIONS Antiphase boundaries. The average domain size in the ordered alloys was found by direct observation to be about 0.25 p. Also, it was observed that the grown-in configuration of antiphase boundaries was changed little by plastic deformation, at least up to 6 pct strain. Fig. 1 shows an electron micrograph of a thin foil of partially ordered alloy (S - 0.8) after 3 pct strain. The micrograph shows a few dislocation pairs and a somewhat crystallo-graphic network of antiphase boundaries. The normal to this foil was found by diffraction analysis to be approximately 11121, with principal directions in

Jan 1, 1962

By Pol Duwez, Spencer R. Baen

A LTHOUGH the practical importance of Fe-Cr--iV Mo alloys has long been recognized, constitution studies have been limited to a few alloys within rather narrow ranges of composition. The purpose of the present study was to establish the phase boundaries in the ternary diagram at a temperature of 1200°F (650°C).* The identification of phases and the determination of phase boundaries were based primarily on X-ray diffraction measurements and occasionally on microscopic observation. The methods used for locating the phase boundaries were essentially those described in detail by Andersen and Jette,' and by others.', The compositions of 180 alloys, prepared by powder metallurgy techniques, are shown in Fig. 1. The chemical analysis and mesh size of the powders which were used for the preparation of the alloys are given in Table I. The powders were mixed for 48 hr or longer, then compacted under 80,000 psi in a %-in. diam steel die. Each specimen weighed approximately 5 g. The compacts were sintered for 4 hr at 2500°F (1371°C) in an atmosphere of pure dry hydrogen (dew point near the temperature of liquid nitrogen). An open tray of chromium powder was placed upstream of the compacts to act as a "getter" for the last traces of oxygen or water vapor. In many cases this chromium powder was bright after sintering. Occasionally the upstream side of the powder was slightly greenish, but in all cases the downstream side was metallic. Some of the alloys contracted during sintering and some expanded as much as 20 pct. The latter alloys, which in all cases were brittle, were crushed in a tool steel mortar, repressed, and resintered for 4 hr at 2500°F. After sintering, the alloys were aged for ten days at 1200°F (650°C) in evacuated (105 mm Hg or better) fused silica tubes and were cooled rapidly to room temperature following the aging treatment. The use of the powder metallurgy technique in preparing alloys for structural investigation offers a simple method 'of avoiding contamination or non-homogeniety which could result from a melting operation. It is very often possible to dispense with chemical analysis of the alloys which have been prepared by the powder metallurgy method. In lieu of chemical analysis, it is necessary to determine the weight of the compact before and after sintering. The chemical composition of the alloy may be considered as that of the green compact, within the limits of accuracy determined by the loss of weight during sintering. In phase-diagram studies it is important to achieve homogeniety in structure, whether the alloys are prepared by powder metallurgy or by melting. Homogeniety means complete diffusion during the sintering of the alloys which are prepared by powder metallurgy. It has been found from experience that the best criterion for establishing the completeness of diffusion is the sharpness of the X-ray diffraction patterns. This criterion has been used throughout the present study. The X-ray diffraction data were obtained using powder cameras of either 214.86 or 71.62 mm diam. Copper, cobalt, or chromium Ka. radiation was used, the choice being based on the alloy composition. The powder samples were obtained by filing or crushing, depending on whether the alloy was ductile or brittle. In some cases, the powder was annealed for 4 to 6 hr at 1200°F in vacuum. The measurements were corrected for film shrinkage and absorption. The large camera, in which the film is mounted

Jan 1, 1952

By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By Howard Martens

HARDNESS behavior of commercial titanium alloys following various heat treating processes has been studied for some time. However, the hardness of such alloys following a definite measured cooling rate from the single phase region has not been reported. Therefore, a series of experiments was conducted on the three alloys: 150A, 130A, and 130B. The manufacturers gave the following compositions for these alloys: Ti 150A: 0.045 pct C, 0.069 pctN, 1.32 pct Fe, and 2.68 pct Cr; RC 130A: 0.13 pct C, and 7.9 pct Mn: RC 130B: 0.11 pct C, 3.5 pct Mn, and 3.2 pct Al. A method similar to that described by Greninger was used, and the cooling rate varied from 6" to 9200°F per sec. The cooling curves were recorded on a Speedomax or a recording oscillograph, and the hardness was measured on a Tukon hardness tester using a Knoop indentor with a 500 g load. The curves of Fig. 1 show the variation of the Knoop hardness with the cooling rate for these three alloys. The alloys 150A and 130B behave in a similar manner, as shown by the curves. In neither of these alloys was it; possible to retain the high temperature ß phases, even by the most rapid cooling rate. The slow cooling rates produced a typical ß structure in these two alloys. As the cooling was increased, these phalses became more finely dispersed and the hardness increased. This increase in hardness with cooling rate continued for the 150A alloy until a rate of approximately 1000°F per sec was reached. At this cooling rate, the structure showed the result of the dif-fusionless transformation of the ß solid solution to the supersaturated a solid solution which is referred as a'. At higher cooling rates, the structure showed no change and the hardness showed no great change, as indicated by the dotted portion of the curve in Fig. 1. The increase in hardness with cooling rate for the 130B alloy continued until a rate of approximately 300°F per sec was reached. At this rate the structure was produced and the maximum hardness was reached. Higher cooling rates caused no marked changes in hardness or structure. The alloy 130A behaved in a different manner, as shown by the curve of Fig. 1. The structure produced by the slow cooling rates was a typical a+ß structure, which became finely dispersed as the cooling rate increased. The hardness increased with cooling rate and reached a maximum at approximately 120°F per sec. At this maximum hardness, the structure showed the result of the decomposition of the ß phase into the ß + phase structure. As the cooling rate was increased, smaller amounts of the at phase were formed and the alloy became softer. For cooling rates of 3000°F per sec and above, the high temperature ß phase was retained and the hardness of the alloy did not change markedly. Acknowledgment This paper presents the results of one phase of research carried out at the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. DA-04-495-0rd 18, sponsored by the Dept. of the Army, Ordnance Corps.

Jan 1, 1957

By C Gunther

The purpose of this book is to present the practical side of economic geology concisely and in convenient form; established facts and the applications of accepted views are emphasized; theoretical discussions and questions of genesis are avoided. Coal, iron, and placer deposits are omitted; they are subjects of specialized study that are fully and concisely treated in other works. The reader is assumed to possess a knowledge of mineralogy, petrography, and elementary geology. The arrangement adopted is based on Kemp's theory of magmatic waters, on Lindgren's conclusions on hydrothermal and secondary alterations, and on the theories of secondary enrichment enunciated by Emmons and Weed. No general classification of ore deposits is attempted, nor is any attempt made to fill by hypothesis the wide gaps, nor to explain the apparent contradictions that rank economic geology among the most inexact of sciences. The present knowledge of the subject is too incomplete to warrant such broad generalizations. The demand for good properties generally exceeds the supply. While mines of the first rank will undoubtedly be discovered from time to time, it is probably true that a great proportion of deposits having outcrops of commercial grade or of evident promise have been recognized and explored. A review of mining conditions over long periods shows that the rich discoveries belong to pioneer days, and that as time goes on the more important developments are the result of lower working costs, improved metallurgical processes, and an increasing knowledge of economic geology. As engineers in search of developed mines no longer expect to find properties having positive ore of greater net value than the price asked, so those in search of prospects should not expect to

Jan 1, 1932

By Fred C., Fred C. Bond

Comminution energy is principally energy of deformation before breakage, which appears as heat. An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories are compared.

Jan 1, 1950

By Fred Mosley

The present operation is located on Whitewood Creek about two miles downstream from Deadwood, South Dakota. Early day placer gold operations took place on this creek from Crook City to an area several miles upstream from Deadwood. Early discoveries were in the Deadwood area. In this particular zone, much of the early work was accomplished at stream level and at various elevations above. In the original operations, it was not possible to reach bedrock in many places due to the ground water level plus the existence of numerous large boulders in the same area. The bedrock in this area is approximately twenty feet deep, consisting of Cambrian and Ordovician sediments. Shortly after the early operations began, many small lode mines and several larger mines released mill tailings directly into Whitewood Creek. This practice continued for a full century, thereby limiting the amount of clean water available for sluicing. These tailings in the stream carried large amounts of heavy minerals along with the natural heavier minerals introduced from erosion and were immediately caught in the riffle boxes, resulting in the suspension of many small sluicing operations. No large scale sluicing or mining was ever done at bedrock level in this area, resulting in an almost virgin placer gold deposit. The old tailings cover much of the area, contributing an additional deposit carrying appreciable gold values. In recent years, a company known locally as New Era Mining Company attempted with some success to exploit the area at bedrock level. The equipment used included a Marian dragline with. a three- yard bucket, a washing trommel mounted on a 40 ft by 20 ft floating pontoon barge, together with two banks of Humphrey Spirals and a secondary spiral for collecting concentrate from the two primary

Jan 1, 1983

By M. W. Bartley, Hugh M. Roberst

ERRATA In the paper (Mining Technology, January 1943) Page 19, second column. Line 5 should read: of Lower Huronian and Early Middle Huronian. Page 20, second column, line 17. Read magmatic solutions instead of magnetic solutions. In the discussion (Mining Technology, September 1943) On page 2 of this discussion pamphlet there is a typographic error. In the chemical analysis, the first reaction should read: CaCO3 + H2O = CaO2H2 + CO2 AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS

Jan 1, 1943

By Leon W. Dupuy

SUPPLEMENT THESE tables should accompany Figs 6, 7, 8, 9 and 10, respectively. To follow Fig 6: TABLE 2[a]-Drill Rod [ ] To follow Fig 7: TABLE 3-Rod Coupling [ ]

Jan 1, 1947