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By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes' expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers' mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By Rees D. Rawlings, C. W. A. Newey

The aging characteristics of an Fe-11 at. pct Mo alloy have been studied by means of light metallography together with density, Young&apos;s modulus, and hardness measurements. The results were consistent with the precipitation of a single intermetallic compound during aging; overaging was slow relative to that in other iron-based binary alloys. The solution treatment temperature had a small effect on the rate of hardening whereas deformation prior to aging had a marked effect on both the rate of hardening and the peak hardness. The density data indicate that the compound precipitated is Fe3MO2 and not the Laves phase Fe2Mo. Analysis of the modulus and density results gave values for the time exponent for precipitate growth of approximately 1.0 and 1.5 for the alloy aged with and without prior deformation, respectively. DETAILED studies of precipitation hardening in bcc matrices have been confined largely to the effects of carbides and nitrides. In view of this and the growing technological interest in intermetallic compound strengthening, e.g., in maraging steels, a study of precipitation in iron-based alloys with a low interstitial content has been undertaken. This paper is concerned with the aging behavior of an Fe-11 at. pct Mo alloy; the mechanical behavior of the alloy will be reported later. The early work of sykes on Fe-Mo alloys showed that precipitation of the intermetallic compound was accompanied by an increase in hardness and a decrease in volume of the material. More recent surveys of the strengthening associated with precipitation have been made3-5 and, in particular, Elsen and wassermann4 showed that deformation prior to aging increased the rate of hardening. These latter workers also followed the precipitation process by means of dilatometry, electrical resistivity, and lattice parameter measurements. Their results confirmed that there is a decrease in volume on aging. Except for the work of Hornbogen on an Fe-20 at. pct Mo alloy, neither clustering nor the precipitation of a nonequilibrium phase has been observed in Fe-Mo alloys. Studies of alloys of lower molybdenum content475 indicate that the equilibrium intermetallic compound is precipitated during aging. However, there is some doubt concerning the nature of the equilibrium precipitate phase. According to the phase diagram constructed by Hansen,8 the phase should be precipitated. This phase has a rhombohedra1 crystal structure which is characterized by the formula Fe706,&apos; although the composition of the molybdenum-rich boundary corresponds approximately to Fe3Mo2. The version of the diagram proposed by Sinha, Buckley, and Hume-Rother indicates that the A phase, a Laves phase Fe2Mo, should be precipitated. Their observation of a Laves phase supports the earlier findings of Bechtoldt and Vacher,13 although, in a recent study of the system by means of diffusion couples, Rawlings and Newey did not detect the phase. The work presented here describes the effect of solution-treatment temperature, aging temperature, and prior deformation on the aging characteristics of the alloy as revealed by light metallography together with hardness, density, and Young&apos;s modulus measurements. In addition the density data are used in an attempt to determine the compound precipitated during aging. EXPERIMENTAL PROCEDURE A 29-kg ingot of the alloy was cast at R.A.R.D.E., Fort Halstead, from deoxidized, Japanese electrolytic iron and sintered molybdenum. The ingot was homogenized for 6 hr at 1473°K and then worked, with intermediate anneals, into 6- and 16-mm-diam rods and 6-mm plate. Chemical analysis of the alloy gave, wt pct: Mo, 17.5 (11 at. pct); C, 0.003; Si, 0.002; S, 0.005; P, <0.002; and02, 0.0098. Solution treatments were carried out under a dynamic argon atmosphere in a vertical, "crusilite" element, furnace which had a facility for rapid quenching into iced water. Except for the study of the effect of solution treatment temperature, all specimens were solution-treated at 1573" * 2°K for 1 hr. Salt baths were used for the aging treatments. Specimens for hardness, density, and Young&apos;s modulus measurements were produced, after heat treatment, from the stock rod or bar using a precision silicon carbide slitting wheel. As described later, the quenching treatment produced local plastic strain in the stock material; consequently, care was taken to ensure that the specimens were not prepared from these regions. Those specimens used in the studies of the effects of prior deformation on the aging behavior were strained in compression in a Denison universal testing machine. Specimens for light metallographic observations were mechanically polished on successively finer grades of diamond paste down to and then etched in either alcoholic ferric chloride or in a 2 pct nital solution. Vickers diamond pyramid hardness data were obtained using a 30-kg load. At least five impressions were averaged for each determination. Density measurements were made using a displacement technique in which each specimen was weighed in air and in dibromoethane at 296°K. The specimens were cylindrical and weighed 3 to 4 g; all weighings were made on a balance reading to 1 x 10"5 g. For each specimen the mean value of five weighings was used to calculate the density. The density of the dibromoethane was determined using the displacement procedure and a standard nickel specimen. The error in an absolute density value was estimated to be HI.01 pct. To obtain the density as a function of aging time a single specimen was used and the density meas-

Jan 1, 1969

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?&apos;, phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?&apos; layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.&apos; The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of &apos;composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert&apos;s-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.&apos; The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

IN a previous article&apos; the authors outlined a study of the variables in rod milling and also reported data from a series of open circuit grinding tests on a massive limestone in a 30-in. x 4-ft end peripheral discharge rod mill. As a second part of the experimental program, an analysis is now presented for the 30-in. x 4-ft overflow rod mill grinding under identical conditions, except that discharge ports on the periphery of the mill shell have been sealed so that the products from the present series overflowed through a 9-in. diam .opening in the center of the end plate. A variance analysis has been made of the combined data for the two experiments, and performances of the two mills are compared here. Included in the first report&apos; were descriptions of feed preparation, rod mill circuit, instrumentation and controls, and techniques used to evaluate data. Dependent and independent variables were defined, and variance analyses were made to test the relative significance of variables and to establish magnitude of error for the experiment. Significant data were plotted in various combinations, and conclusions were drawn from the graphs. The procedure and analysis in this series of tests follows the first tests and is not repeated. Data from the second series are recorded in Table I. Listed in the first three columns are the independent variables of feed rate (1000, 2000, 3000, 4000, and 5000 1b per hr), mill speed (50, 60, 70, 80, and 90 pct of critical), and pulp density (50, 60, 70, and 80 pct). The dependent variables, Pso, P100, reduction ratio, slope of the log-log sieve analysis curve, power demand, and Bond work index follow. Of these, only the reduction ratio and the Bond work index were analyzed for significance. Production of new surface as calculated from sieve analyses has not been included for this series because of the questionable assumptions that have to be made to satisfy the formulas involved. The large number of products obtained during the runs precluded the use of surface measurement techniques by the gas adsorption methods at this time; however, samples of all products have been stored for future reference. To test the consistency of the reporting of the sieved products, an averaged sieve analysis was calculated from the wet-dry plots obtained from the three product samples of each run. The resulting averaged analysis was plotted and the P80, selected. The relative deviations of the P80&apos;s from each of the three product samples with respect to the P80 of the averaged analysis were then calculated. In only two sets were the relative deviations (6.2 and 9.9 pct) considered excessive. In each of these two sets, one sieve analysis was obviously out of line; hence that analysis was ignored and new averages were computed. This reduced the relative deviations to 1.2 and 2.7 pct respectively. The relative deviations of the product analyses with respect to their averages ranged from 0.1 to 1.4 pct at 1000 lb per hr, 0.0 to 1.1 pct at 2000 lb per hr, 0.2 to 3.0 pct at 3000 lb per hr, 0.3 to 4.3 pct at 4000 lb per hr, and 0.5 to 5.2 pct at 5000 lb per hr. The relative deviation of the 80 pct passing point for 96 dry sieve analyses of the feed with respect to that of the averaged analysis was 7.6 pct. This slightly higher percentage can probably be attributed to a greater proportion of tramp oversize in a crusher product than is ordinarily found in a rod mill product. The last column on Table I lists the adjusted work index, which has been used as the measure of efficiency for the various combinations of operating conditions investigated. Efficiency increases as the index becomes lower. It was reported in the previous paper that the work indexes for the Waukesha limestone used in these experiments decreased as the product size decreased (as calculated from Bond grindabilities). That is, this limestone becomes easier to grind as the material becomes finer. This is unusual, because the work index for most materials as calculated from the Bond grindability has remained constant as the product size decreased or has increased slightly. Table II lists the results of Bond grindability tests at all mesh sizes from 3 to 200 and the work indexes calculated from them. To remove this variation of work index with product size from the data so that results would apply to any material of constant work index, the work index values shown in Table II were plotted against product size on log-log paper. From this curve (a straight line function in this case), the expected work index for the product size for each of the runs of the experiment was obtained. The work indexes as calculated from the reduction ratio and energy consumption were then divided by the corresponding expected work index. The results obtained are reported in percentages on Table I as adjusted work index and are actually percentages of the work index for the Waukesha limestone at the size in question. Multiplication of the work index value for a material of constant index by these percentages should allow the application of the adjusted work index curves to the material. Only the adjusted work index values, not the actual experimental values, were used for the variance analyses and for the graphs.

Jan 1, 1956

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the &apos;a; and &apos;c,,&apos; edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.&apos; LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By R. W. Carpenter, J. C. Ogle

It is possible, by using pack-rolling instead of conventional rolling, to reduce a number of metals to thicknesses of 2µm or less. Such thinfoils are generally made at room temperature without intermediate annealing. In addition, pack-rolled foils fail by developing pinholes at thicknesses near 2µm instead of developing the shear cracks usually observed in cold-rolled ductile metals. This paper presents the results of a general investigation of the deformation substructure and texture developed in copper and iron pack -rolled from 130 to about 2µm thickness. Electron microscopy showed that in both metals a fine (0.2 to 0.5?µ m) deformation subgrain structure formed during pack-rolling; in neither case was this substructure grossly different from substructures formed during conventional rolling. The deformation texture formed in pack-rolled iron was quite similar to usual bcc textures; however, in the case of copper, the cube texture was stable during pack-rolling and the normal copper deformation texture was unstable. It is shown analytically that the constraining pack induced a large hydrostatic pressure in the foils during pack-rolling. The pinhole failure mechanism is attributed to the presence of the large hydrostatic pressure during pack-rolling; this strongly suppressed the growth of shear cracks. The stability of the cube texture in copper is also probably due to the unusuul stress distribution developed during pack-rolling. EXPERIMENTS at several laboratories have shown that very thin foils of the common structural metals and many of the rare earths can be made by "pack-rolling". 1-3 The technique was originally developed to make specimens for nuclear scattering experiments and foils for X-ray filters. It is also useful for making experimental laminar metallic composite bodies and foils thin enough for direct examination by ultra-high voltage electron microscopy without the need for special thinning techniques. Pack-rolling in the present context means a three-layer pack, with the material to be rolled into foil comprising the center layer. The outer two layers, which constrain the foil during reduction, are ordinarily austenitic stainless steel. Typically, a 130 µm (0.005 in.) metal strip can be reduced to a final thickness of 2 µm or less by this process. This is accomplished at room temperature, without intermediate annealing. It has been observed that foils produced by this process do not exhibit at any stage of their reduction the severe work-hardening found in strip rolled by conventional cold-rolling methods. Neither is the failure characteristic the same."&apos; Conventionally cold-rolled ductile metal strip fails by developing shear cracks on planes whose normals nearly bisect the angle between the rolling direction and normal to the rolling plane; these are planes of maximum shear stress. In pack-rolling this mechanism has not been observed; failure occurs by the formation of pinholes on the foil surface (penetrating the foil). If pack-rolling is continued the hole density increases. These differences in behavior imply the existence of appreciably different substructure in pack-rolled foils compared to substructure in conventionally rolled material, or perhaps that the geometry of pack-rolling has an effect on the foil behavior. This paper describes an investigation of deformation substructure and texture in some specimens of pack-rolled copper and iron, and some considerations of the stress distribution in the foils during rolling that result from the geometry of pack-rolling. EXPERIMENTAL DETAILS Three different materials were used for pack-rolling in the present work: soft copper sheet (99.8 pct Cu, 0.03 pct 0, electrolytic tough pitch) and two types of iron, Ferrovac E* and Armco iron. Each was "Crucible Stccl Co. initially in the form of 130 µm annealed strip with grain size ranges of approximately 10 to 40 µm. The initial texture of the copper (determined as noted below) was the normally observed cube type (001)[100]; there was evidence of a small amount of material in the cube-twin orientation reported by Beck and Hu.4 The initial texture of the Ferrovac E was similar to that reported for recrystallized iron by Kurdjumov and sachs,5 who list the principal orientations as {111}<112>, {001}<110> 15degfrom RD and a weak component {112}(110) 15 deg from RD. The starting texture of the Armco iron was not determined. Pack-Rolling Procedure. A four-high mill was used for all specimens. The work roll and backing roll diameters were 1.625 and 5.25 in., respectively. The peripheral roll speed of the work rolls was about 2.5 in. per sec. All foils were initially reduced from 130 to 100 µm by conventional straight rolling and then inserted into a pack, without any intermediate annealing, for further reduction. The pack consisted of an 0.033 in. (838 µm) thick 3 by 6 in. polished sheet of austenitic stainless steel, folded to make a 3 by 3 in. jacket. After folding, the jacket was given a small reduction to close the fold tightly before insertion of the foil. During pack-rolling a constant change in roll spacing was made every third pass. The roll-spacing change corresponded to a 5 pct reduction in thickness for a new pack. This approached a 10 pct reduction when the pack had decreased to about half its original thickness. At this point the deformed pack was discarded and a new one

Jan 1, 1970

By G. R. Leverant, C. P. Sullivan

Re crystallized TD-nickel mi-2Th0,) in both coated und uncoated conditions was fatigued at 1800°F at total strain ranges varying .from 0.2 to 0.75 pct. The fatigue life of uncoated inaferal, Nf, was related to the total strain range, ?eT, by (2Nf/021AeT = 0.014. A duplex Al-Cr pack coating increased the fatigue life by about a factor of two. The cracks that led to failure in both coated and uncoated material were initiated at the outer surface, indicating that the mechanical properties of the surface layers were important in determining fatigue life. Crack propagation and subsurface crack initiation in the TD-nickel occurred preferentially at grain boundaries with cavitation at thoria particle-matrix interfaces an integral part of the grain boundary fracture process. The importance of both the grain morphology developed during thermome chanical processing of TD-nickel and the distribution of thoria particle sizes to fatigue resistance are discussed. THE fatigue properties of only a few dispersion-strengthened metals have been studied at temperatures 0.5 Tm;1,2 among these have been lead and aluminum containing oxide dispersions. TD-nickel is a material of interest for application in aircraft gas turbine engines, but little fundamental information is available on its behavior under cyclic loading conditions. In this study, the low-cycle fatigue properties of TD-nickel were determined at 1800°F with emphasis on the 101-lowing; 1) the relation of the grain morphology produced during thermomechanical processing to crack initiation and propagation; 2) the role of thoria parti-cles in the fracture process; and 3) the effect of an oxidation resistant coating on fatigue life. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in. thick plate which had been subjected to a proprietary series of thermomechanical treatments with a final anneal at 2000°F for 1 hr in hydrogen. The composition of the material is given in Table I. At the test temperature of 1800°F, the 0.2 pct offset yield stress was 15,000 psi, and the elongation and reduction in area were 4.6 and 3.0 pct, respectively. The microstructure of this material has been previously described.&apos; Briefly, it consists of an array of lath-shaped grains, about 0.15 mm in thickness, with the long dimension of each grain parallel to the primary working direction, Fig. 1(a). The presence of very small annealing twirls, Fig. l(b ), together with the absence of extensive dislocation networks, Fig. L/C), indicated that the material was in the recrystal- Table I. Composition of TD-Nickel ThO2 2.3 vol pct C 0.0073 wt pct lex 0.01 wt pct Cr 0.01 wt pct Cu 0.004 wt pct S 0.001 wt pct Ti <0.001 wt pct Co <0.01 wt pct Ni bal lized condition. Commercial TD-nickel sheet has a similar grain size and shape, but unlike the present material is not recrystallized as evidenced by the absence of annealing twins and the presence of a well-developed dislocation substructure.4 The plate material had Young&apos;s moduli in the rolling direction of 22 x 106 psi and 13 x 106 psi at room temperature and 1800°F, respectively, indicating a texture with a strong {100}<001> component in agreement with previous observations on recrystallized TD-nickel sheet.596 The 2.3 vol pct of thoria particles were uniformly distributed although some clustering and stringering of larger particles was occasionally seen. The average diameter of the particles was 450 and the calculated mean planar center-to-center spacing was 2100Å. Two specimens were coated with a duplex A1-Cr pack coating. The coating was somewhat nonuniform from one position to another along the gage length. An area of the coating after testing is shown in Fig. 2. Electron microprobe analysis revealed the following zones in the various lettered regions indicated in Fig. 2: A) a bcc matrix of B-NiA1 with some chromium in solid solution along with a fine dispersion of a chromium-rich second phase which was probably precipitated during cooling from the test temperature to room temperature; B) fcc y&apos;-Ni,Al with some chromium in solid solution; C) porosity; D) a two-phase mixture of a chromium-rich solid solution containing nickel and aluminum and a small volume fraction of a nickel-rich solid solution having approximately the same composition as the immediately adjacent portion of region E, E) the TD-nickel substrate containing chromium in solid solution to a depth of 5 to 10 mils. As expected from the nature of the diffusion processes involved,7 the thoria particles were present only up to the layer of porosity, region C, Fig. 2. The measured thickness of the coating proper, zones A to D, after testing was 1 to 2 mils. The specimen design and testing techniques have been previously discussed.&apos; Stressing was axial and parallel to the lath-shaped grains (i.e., parallel to the rolling direction). The total strain range was controlled between zero and a maximum tensile strain varying from 0.2 to 0.75 pct. (The test at 0.2 pct total strain range was switched to load control at 1030 cycles at which point the peak tensile and compres-

Jan 1, 1970

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU.,O, was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU3O8 with an accuracy of ± 10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU3O8 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry. Design and Construction: Three methods of detecting radioactivity were considered and applied in developing the core scanner now in use: 1) the Geiger tube, 2) liquid scintillation phosphors, and 3) solid scintillation phosphors. The desired sensitivity and long-term drift characteristics needed for this operation could be attained only by using solid scintillation phosphors. All three methods are discussed. Before scintillation counters were common, nine beta-gamma sensitive Geiger tubes 7/8 in. diam by 12 in. long were used, arranged to surround the drill core with tube axes parallel to the axis of the core. This arrangement of Geiger tubes was en- closed in a lead shield 1 in. thick, and provision was made to slide a 6-ft length of drill core manually into the counting chamber, one foot at a time. A count for each segment was taken with a scaler while the core remained stationary. The equivalent uranium content of the different sections of drill core could then be estimated with the aid of a calibration curve of counts per unit time vs percent equivalent uranium (eU). In rare cases the effects of the radioactivity concentrated in small areas within the core introduced errors in the readings made with the Geiger tube arrangement owing to the geometry of the measurement. The variability of counting rate due to a localized concentration of radioactivity in a spot in the wall of a drill core is illustrated in Fig. 1. This effect and the inherent low efficiency of the Geiger tube were considered major disadvantages of this counting arrangement. When liquid scintillation phosphors became available the core scanner in Fig. 2 was constructed to make a more accurate measurement of the equivalent uranium content of a sample. This instrument contains about 4 liters of liquid phosphor in a stainless steel coaxial cylinder 1 ft long, with inner and outer walls 0.060 in. and 0.125 in. thick, respectively. Four end-window type photomulti-plier tube with cathodes of 2 in. diam, immersed in the solution at right angles to the axis of the core, were used to observe light flashes in the phosphor. The liquid phosphor offered equal sensitivity to radiation originating at any point in the enclosure and represented geometrically the optimum in design. However, providing a semi-permanent leak-proof seal between the glass envelope of the phototube and the metal walls of the container proved to be a serious problem in constructing the equipment. The most effective seals were especially machined O-rings from sections of large tygon tubing. The tygon took a permanent set owing to cold flow characteristics and in most cases sealed completely. The light absorption characteristics of the liquid phosphor changed gradually with time, and after one month the counting rate had decreased to half the original value. The most sensitive liquid phosphor tested proved to be a solution containing 4 g of 2.5-diphenyloxazole and 0.01 g of 2-(1-naphthy1)-5-phenyloxazole per liter of toluene. With fresh solution in the chamber and with all photomultiplier tubes operating in parallel, the counting rate contributed by any one of the four photomultiplier tubes was about 85 pct of the counting rate from a single tube operated individually. From these observations it was concluded that owing to coincident loss and light attenuation within the liquid phosphor, the apparent sensitivity could not have been materially increased by additional phototubes. However, this approach to core

Jan 1, 1960

By Ernest O. Kartinen

This report is the accumulation of eight years of experience on only one small phase in the business of oil production. It is not intended as a final report but rather as a progress report dealing with the internal corrosion of oil field dehydrating tanks. The corrosion of dehydrating tanks continues to be a problem in the production of crude oil. The deterioration hy corrosion of these tanks falls into three general classifications: (1) Atmospheric corrosion of exterior areas, (2) corrosion of the underside of deck and the rafters and top area of the upper row of staves in that part of the tank which is known as the vapor space, and (3) corrosion of the bottom and shell areas, and the steam coils which are normally immersed in water and thus exposed to the corrosive action of the water. Atmospheric corrosion is primarily a paint problem, and has been omitted in this discussion. The corrosion in the vapor space, in this company&apos;s experience, which has been of great concern only in one area. has also been omitted in this discussion. The third, and most troublesome type of corrosion, and the one with which this report deals, is that which occurs in the water-exposed areas of dehydrating tanks, and, to a lesser degree. in some stock tanks. The operating temperature of these waters varies from 80°F to 160°F and the salt counts run from a few thousand to as high as 25.000 parts per million. Corrosion in these tanks occurs in three forms: (1) pits, (2) ringworm type of attack along the vertical and horizontal bolt seams, and (3) as a general attack, spread over a wide area. Steam Coils In dehydrating tanks, our experience has been that the steam coils are the first to show signs of corrosion, and then the shell and bottom areas. This action is not uniform throughout this company&apos;s operations. Some installations have coil troubles with very little tank trouble, and some show just the opposite. But in the majority of cases the coils are the more seriously corroded areas. This may be partly due to the fact that we have tried by periodic application to keep a protective coating on the interior areas of the tanks, and some protection has been afforded by these coatings. Through the years several types of hot and cold coatings have been tried with many various methods of cleaning the steel, ranging from use of cleaning solvents to hot and cold Oakite washes, as well as sandblasting. Although experience has shown that a longer life expectancy of a coating is possible after a very thorough steel cleaning job, it has still been necessary to recoat these tanks at least every two or three years. Until a few years ago, vertical spiral steam coil bundles were installed when the tanks were originally erected. When these coils needed replacement, in some cases within 18 months, it was necessary to remove a couple of shell staves to accomplish this task. This required a down time period of several days and was often very inconvenient to the production operations of the leases. This problem was considered on the basis that the coils were expendable, and thus. to eliminate any unnecessary down time when changing coils, the vertical spiral coils were discarded in favor of horizontal flat coils which could be taken in and out of the tanks by way of the cleanout openings, and put together with unions. This made a fairly easily replaceable and repairable coil. But it was still very much of a nuisance when repairs were necessary. Efforts to increase the useful life of the dehydrating tanks led to the adoption of galvanized tanks at an increased initial cost. The zinc coating was depended upon for protection and no other protective coatings were applied. In July, 1944. during the development of a new lease, a 3-ring 1,500 bbl, black iron water tank was converted into a dehydrating tank with steam coils to handle the new production. This tank was coated inside with a cold, brushed-on coating, for protection against corrosion. After approximately 18 months of service, holes developed in the tank and the steam coils. The tank was emptied and cleaned for repairs. The coils were so badly pitted that it was felt advisable to replace them. Coating Becomes Loose Inspection of the tank showed the protective coating to be still in place but loose, and numerous blisters were in evidence. A closer inspection showed that the interior of this tank was so badly pitted under the coating that any further attempt to use the tank was inadvisable. This tank was therefore discarded and a new galvanized tank ordered and set up at considerable expense and inconvenience. In April, 1946, another dehydrating tank installation was made on an adjoining lease. This installation consisted of a 1,500 bbl. 3-ring galvanized tank with two sets of flat steam coils 12 in. and 24 in. up from the bottom. In September, 1947. seventeen months after installation. salt showed up in the boiler feed water. When the dehydrating tank was opened and cleaned, the steam coils were found to be badly pitted — several holes having penetrated through the wall of the pipe. New coils were installed.

Jan 1, 1950

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;&apos; and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.&apos; Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively&apos; from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)&apos; which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

H. Schwartzbart and W. F. Brown, Jr.—The authors have divided the effects of recovery on the true stress-true strain curve into two types; metarecovery, which effects only the first part of the curve or the yield strength, and orthorecovery, which effects the flow stress at any strain. Both of these are said to be true recovery effects, involve no recrystallization, and are explained by the removal of two different types of imperfections caused by work hardening. However, there seems to be some question as to whether the data are sufficiently conclusive to exclude, as an explanation of the authors&apos; results, a mechanism based on the relief of residual stresses between the grains or slip bands and recrystallization. It appears that metarecovery could be interpreted in the same fashion as a customary interpretation of the Bausch-inger effect. The balanced system of internal stresses which exists between grains in a strained specimen due to varying orientation and, hence, yield strengths, of the different grains is responsible for a reduced yield strength in compression following pre-tension, and, similarly, for an elevated yield strength in tension following pre-tension. If the specimen is now heated so that the internal stresses are relieved by creep, then the yield strength in tension following tension will have been reduced and in compression following tension will have been raised. There seems to be a very strong case for the lack of recrystallization in the aluminum investigated by the authors, if one defines recrystallization as the presence of visually detectable new grains or accepts the X-ray evidence as conclusive. One must remember, however, that the appearance of spots on the back-reflection X-ray patterns cannot be taken as the time when recrystallization first started. The areas of recrystallized strain-free material must first have grown to a size large enough to give distinct spots on the patterns and this may take some time. Averbachl7 in an investigation of brass has shown that recrystallization can be detected by extinction measurements at temperatures lower than those based on hardness or X-ray line width determinations. It can be seen from fig. 10 that the rate of recrystallization is extremely low over a considerable time period at the onset of the process. Observations on the rate at which small amounts of recrystallization effect the flow stress would have given further insight as to whether undetectably small amounts of recrystallization might have been responsible for orthorecovery. Also, the question arises as to whether the effects observed in fig. 6 for various times and temperatures could not have been obtained if the time at 212°F were sufficiently long. In addition, the argument that the curve in fig. 10 is not sigmoidal seems weak in view of the scattering of the points. It is conceivable that an accurate determination of the curve for the first 100 hr would exhibit a relationship other than the one drawn. There is one point we would like to raise about the condition of the starting material. The authors annealed their material at 750°F for 15 min to remove the effects of any previous work hardening or machining strains. Reference to the work by Anderson and Mehl shows that this treatment may not have completely recrystallized the aluminum, so that the starting material may have had some strained areas. Higher temperatures or longer times may have been required to remove the effects of any small strains. We would like to mention some results of tests being conducted at the Lewis laboratory of the National Advisory Committee for Aeronautics in an investigation of the Bauschinger effect in relation to fatigue. Tests were performed on annealed electrolytic copper and several annealed brasses. Specimens were pre-strained 1 pct in tension and then tested in compression or tension with and without intermediate stress-relieving annealing treatments at 500°F for various times. Specimens heated at 500°F for 10 1/2 hr showed an elevation of the flow curve in compression and an approximately equal lowering of the flow curve in tension when compared with the curves for the un-heat treated specimens. After approximately 0.8 pct strain, all flow stresses coincided and were equal to the flow stress of the virgin material at this strain. This behavior is consistent with the metarecovery observed for aluminum by the authors and for which a residual stress model can be used. On the other hand, increas-

Jan 1, 1951

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

WITH the greatly expanding use of magnesium during the war, it appeared necessary to the War Metallurgy Committee that procedures of heat treating common magnesium casting alloys be investigated systematically. Accordingly, the National Defense Research Committee of the Office of Scientific Research and Development placed a research contract with the University of California, supervised by the War Metallurgy Committee. Research on the solution heat treatment and aging of magnesium alloy AZ92, (formerly ASTM No. 17; also known as Dowmetal C or AM260) which was done under "Restricted" Project NRC-21, in 1942-1943, and reported, in detail in a final report to the OSRD on September 3, 1943, is the basis of this paper, which has been released for publication by the OSRD. American experience with magnesium alloys prior to World War II was limited, although some of these alloys had been in commercial use since 1909. Requirements of the aircraft industry for light alloys made it imperative to understand and utilize the advantageous strength-weight properties of magnesium castings. Magnesium casting alloys are commonly solution heat treated to increase their ultimate tensile strength and ductility; this treatment may be followed by an age hardening at elevated temperatures, which raises the tensile yield strength but diminishes the ductility. In the present investigation, AZ92 was studied to determine the effects on properties of various solution heat treatment and aging schedules. The principles of heat treatment of magnesium alloys are the same as for other non-ferrous alloys. The alloy studied, AZ92, has a nominal composition of 9 pct aluminum, 2 pct zinc, and minor constituents. Fig I shows, by the projection of isothermal sections on the concentration plane, the solubility surface1 of the ternary magnesium-rich solid solutions as determined by X ray analysis. From this figure it may be seen that above approximately 375°C (707°F), AZ92 alloy is a single phase alloy at equilibrium; below this temperature the equilibrium condition is a. two phase alloy. The beta constituent which precipitates from the solid solution exerts a hardening effect. Because the zinc concentration is only 2 pct, and because of its solubility relations, AZ92 resembles a binary alloy of magnesium with aluminum. The solubility curve1 of Fig 2 shows how rapidly the solubility of the beta phase decreases with decreasing temperatures. Unlike many aluminum alloys, magnesium alloys do not age harden at room temperatures; precipitation hardening of AZ92 alloy is performed at about 177°C (350°F). At this temperature about 3 pct aluminum

Jan 1, 1947

By D. J. McAdam, R. W. Mebs

The technical cohesive strength of a metal means, not the interatomic forces, but the technically estimated resistance to fracture. An example of such resistance to fracture is the so-called "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. According to the prevalent view,8 the technical cohesive strength of a metal. in any particular state as regards prior mecharlical treatment and heat-treatment, is determined by a limiting value of the algebraically greatest principal stress. In two previous papers by one of the authors, evidence was presented to indicate that the technical cohesive strength of a metal cannot be represented by a single stress value, but that it comprises an infinite number of values corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength thus comprises an infinite number of technical cohesion Limits, each representing a specific stress combination at fracture. In the same papers, evidence was presented that plastic extension causes a continuous increase in the technical cohesive strength. Such a variation is not in accordance with the prevalent view that plastic extension first increases, then decreases, the technical cohesive strength.&apos; In this paper, as in the previous papers,14.15 the algebraically greatest principal stress will be designated S1, the least principal stress will be designated 33, and the intermediate principal stress will be designated S². The technical cohesion limit under polarsymmetric tension (S1 = S2 = S3) will be termed the "disruptive stress," and the cohesion limit under unidirectional tension (S2 and S3 = o) will be termed the "severing stress."l4, .l5 The yield strength of a metal, according to the generally accepted theory, may be represented by a constant value of the shearing-strain energy, and hence by a constant value of the sum of the squares of the three principal stress differences. In the second of the previous papers,15 however, evidence was presented that the limiting yield stress decreases with increase in the volume stress, the algebraic average Of the three principal stresses.* This in fluence of the volume stress becomes prominent only in the field of triaxial tension. In the two previous papers,".&apos;5 diagrams were presented to show the variation of the technical cohesion limit, yield stress, and ultimate stress with the combination of principal stresses and with plastic extension. Those diagrams and the resultant • Any stress system ma? be resolved into a polarsymmetric stress causing pure volume strain and a combination of pure shearing stresses. which cause no change of volum

Jan 1, 1945

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By J. B. Newkirk, A. H. Geisler

Certain of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some perrnanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems oA&apos;er for study over the usual in which an intermetallic compound is formed are many: 1. Since the precipitate has the same crystal strutture as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be ex. petted to have the same orientation. 3, Small &,registry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from 0 to 100 pet* thus permitting wide freedom for the study of the effect of cornposition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1&apos;2 The two have the same <Jo parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for CU-Ni-CO alloys because of the similarity in constitution but this had not been demonstrated. The Present investigation was conducted on a CU-Ni-CO alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established, however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system Was chosen for a comprehensive investiga-

Jan 1, 1949