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By A. J. Mortlock

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

Jan 1, 1969

By M. J. Marcinkowski, K. S. Sree Harsha

A detailed numerical analysis has been made of the equilibrium configuration of partial dislocations in a blocked deformation twin under an externally applied stress. Twins made up of both pure screw and pure edge partials have been considered. The components of stress in the vicinity of the twin tip associated with each of these configurations have been plotted. It has been found that at some critical degree of oblateness the shear stress fields of the blocked screw or edge twin can both sPontaneously nucleate slip, whereas only the component of stress oxx about the edge twin can nucleate and propagate cracks. TWINNING becomes a predominant mode of plastic deformation at low temperatures and/or high strain rates. Fig. l(a) shows what must be the first step in the formation of a deformation twin, namely the formation of a loop of imperfect dislocation bounding a stacking fault. In an fcc crystal the partial dislocations have Burgers vectors of the type 1/6 a,(112) and the fault is of the intrinsic type while in the bcc crystal the partials have Burgers vectors of the type ao(lll). The stacking sequence of (111) planes in a perfect fcc crystal is given by ABC ABC, and so forth, and in one which contains a twin by ABCABACBA, and so forth. It is apparent that the stacking fault and twin give rise to no mistakes associated with adjacent close-packed planes; however, with respect to second-neighbor close-packed planes the faulted crystal has twice as many mistakes as the twin. The energy of the twin boundary may thus be taken to be one-half that of the intrinsic fault boundary. In the case of the bcc crystal the stacking sequence of (112) planes is given by ABCDEFABCD, and so forth, in a perfect crystal, by ABCDCDEFA, and so forth, in a crystal which contains a fault, and by ABCDCBAF, and so forth, in one which contains a twin. An analysis similar to that applied in the fcc crystal shows that both the fault as well as the twin involve no neighbor violations across adjacent planes. However, there are twice as many violations across second-neighbor (112) planes associated with the fault as compared to that of the twin. Thus once again the energy of the twin boundary may be taken as one-half that of the fault. It is important to note that, unlike the fcc, the faults in the bcc crystal involve first nearest-neighbor violations and are thus expected to be of much higher energy than those in fcc crystals. A more detailed analysis of the material discussed above can be found in Ref. 1. To a good approximation then, the lenticular twin shown in Fig. l(b) can be generated by adding partial dislocation loops on successive (111) planes for fcc crystals or (112) planes for bcc crystals in the manner shown, with no additional expenditure of chemical energy other than that required for the fault shown in Fig. l(a). In practice, deformation twins are much more extended than that shown in Fig. l(b) and more closely resemble one shown schematically in Fig. l(c). It is readily apparent that the free energy of the twin and matrix are identical. In those cases where the partials lead to a structural change, the free energy of the material contained within the dislocation array is lower than that of the matrix and we have the so-called martensite transformation. The present investigation is the first in a series of five major theoretical-experimental efforts which will deal with the static and dynamic behavior of twin nucleation and growth. There has been a recent surge in activity pertaining to the equilibrium shapes of twin lamellae2'3 and

Jan 1, 1969

By R. R. French

Investigations were conducted by the lndiana Geological Survey for some dry methods of bene-ficiating low-grade gypsum ore. Seventy-two batch and continuous flow tests were performed with a roller mill, rod mill, pebble mill, electronic color sorter, electrostatic separator, and an air separator. Approximately 650 size analyses and 550 chemical analyses were performed during the investigation. Batch samples were tested by the Survey, and most of the continuous flow tests were handled by com-mercial laboratories. INTRODUCTION Although many companies producing gypsum have been interested in dry beneficiation, very little information has been published in the past. One of the most comprehensive investigations was reported by the Canadian Department of Mines.5 Other reports of interest have been published by the Canadian Department of Mines,' the South Australian Department of Mines,2 and the U.S. Bureau of Mines.3 Some beneficiating practices, such as hand picking, selective mining, crushing and screening, milling, and air classifying, were already in use in the Canadian industry prior to MacPherson's investigations.5 MacPherson examined the effect of tabling, air separation, screening, flotation, electrostatic separation, calcining, washing, and various types of milling, in his efforts to eliminate dolomite, limestone, and small amounts of silica and clay from the gypsum ore. RAW MATERIAL Gypsum and anhydrite occur within the lower part of the St. Louis Limestone (Mississippian) in southwestern Indiana. Gypsum in single beds 10 or more ft thick occur at Shoals, Martin County; near Freedom, Owen County; near Bloomfield, Greene County; and in the Devonian strata of LaPorte County. Only the Shoals deposit has been exploited commercially. The western edge of the Shoals deposit is contaminated by a continuous bed of shale, about 1 1/2 to 2 ft thick, near the top of the evaporite and by thin continuous strata or irregular masses of carbonate rock. The low-grade material used in these investigations was obtained from the waste pile of the National Gypsum Co.'s plant at Shoals. The waste ore averaged about 67.4% gypsum and was contaminated by various amounts of shale, dolomite, and limestone. All the material had been previously crushed and screened to minus 1 1/4 to plus 3/8 in. X-ray analyses of powdered, sedimentated, gly-colated, and heat-treated samples of the shale showed that it was composed of slightly structurally disordered illite, Fe-rich chlorite, and very finegrained disseminated silt. The clays and silt were partly cemented with carbonate material. Light-gray argillaceous limestone and gray or brown porous dolomite made up most of the carbonate rock contamination. Crushing Characteristics: The rate unweathered gypsum, carbonate rock, and shale reduce in size was determined by crushing handpicked samples in a rod mill and screening at minus 100 mesh (.0059 in.). Fig. 1 graphically represents the data. These data indicate that carbonate rock should be relatively easy to separate from gypsum, but that shale should be difficult to separate from gypsum by differential crushing. Controlled Samples: Eight rod mill tests of hand-picked samples of mixed gypsum and shale and mixed gypsum and carbonate rock were made. Sample weight and crushing weight were standardized, but the scalping screen size was varied from 3 to 10 mesh (.265 to .0787 in.) in order to obtain the optimum purity and recovery. The data obtained from the tests (see Table I) illustrate that the relatively hard carbonate rock allows appreciable beneficiation (13.6 to 18%), but the low strength gypsum and shale allows only minimal separation (3.1 to 7.5%).* Semi control led Samples: During the investigation considerable slaking of the shale was noted when the ore was subjected to alternate wetting and drying. As demonstrated in laboratory tests, as much as 76% shale can be removed by two cycles of wetting and drying in a 48-hour period with subsequent screening at .265 in. Five ore samples, stockpiled and weathered, were screened, rod-mill crushed and rescreened at .157 or .187 in. with excellent results (Table 11).

Jan 1, 1967

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By W. W. Eckles

This paper is presented as a suniniary report of the use of well gas composition correlations obtained from mass spectrometer recordings as a means of identification and determination of reservoir continuity. Conventional methods for detecting composition differences are en-pensive, elaborate, and difficult to obtain. This excludes the use of extensive composition data for most applications. During recent years the mass spec-trometer has come into general use as an analytical tool in petroleum refineries. The use of mass spectrometer composition patterns ir~ characterizing or "finger-printing" the produced gas from a reservoir, presents a novel method for correlatitlg gas samples from well to well. The mass spectrometer provides a trace similar to an electric log. having peaks which represent the abuntlnnce of certaitz hydrocarbons in the well gas sample. Without going further into the detailed analysis the idea has been advanced that these traces or patterns could be used as a means of identifying a particular natural gas. This theory has proven to be essentially correct. The mass spectrometer pattern method is simple and cheap as COi?7pared to other standard methods. It greatly facilitates the solution of reservoir and geological problems in which correlation of well gas Com-positions is a factor. Specific field applications have been made. This paper concerns the results obtained in 465 individual gas analyses from 35 fields and 77 res- ervoirs. In a number of cases it has been found that such data have been extremely valuable in the determination of reservoir continuity. In at least one case, the method was a valuable contribution in tracing a reservoir from sand to sand in a coinplex fnulted field involving n11rnerous gas reservoirs. Field applications are presented to illustrate the possibilities of the method at the present stage of developnient and to stimulate the ernployrnent of this new approach by geologists and petroleum engineers in the industry. INTRODUCTION Identification of producing horizons and the determination of reservoir continuity are often a problem in those areas where dome structures and highly faulted sands are encountered. To complicate the picture further, there may be numerous sands, one on top of the other which dip and diverge in different directions. Even though it may be possible to develop some solutions to the preceding problems on the basis of the geological and reservoir data on hand. it is readily recognized that substantiating data based on independent methods would he extremely valuable. It has been found through field studies that correiation of well gas composition can be used to advantage in the geological and engineering study of a complex reservoir identification problem. METHOD FOR COMPARISON AND CORRELATION OF WELL GAS SAMPLES Since a large number of well gas samples are required in a gas identification or reservoir con- tinuity problem, it is necessary that a method of analysis be employed which can detect differences in composition readily and inexpensively. Although detection would be possible by means of low temperature fractional distillation (POD) analpsis, the method requires a relatively large sample and is comparatively slow and expensive to run. The mass spectrometer affords an inexpensive and precise analysis of small well gas samples taken at the surface which are about 1/300 as large as a POD sample. These samples can be obtained by regular field personnei and shipped to the spectrometer for analysis. It is, therefore, a practical approach to the problem. A typical record from the mass spectrometer is illustrated in Fig. I. The peaks on the record represent the abundance of ions produced from the different hydrocarbon molecules making up the gas sam-ple. In well gas comparisons only five peaks are employed, since the other peaks are formed from the same gas molecules and furnish no additional information. The five peaks used represent the abundance of methane, propane, ethane, butane and heavier, and oxygen. They are referred to respectively as the 16, 29, 30, 43, and 32 peaks. The oxygen peak is used to correct for air content in

Jan 1, 1958

United Engineering Trustees, Inc. W. D. B. MOTTER JR., '44 A. L. QUENEAU, '41 ALBERT ROBERTS, '43 The Engineering Foundation GEORGE D. BARRON, '44 F. F. COLCORD, '42 A. L. QUENRAU, '41 Engineering Societies Library Board A. T. HASTINGS, '41 J. W. LAIST, '44 A. B. PARSONS, EX-Officio T. T. READ, '42

Jan 1, 1941

For the year ending February, 1919 PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. PAST PRESIDENTS L. D. RICKETTS, NEW. YORK, N. Y. PHILIP N. MOORE, ST. Louis, Mo. FIRST VICE-PRESIDENT C. W. GOODALE BUTTE, MONT. TREASURER GEORGE D. BARRON, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 2, 1919

By O. M. TUPPER

REQUIRING a finer ground clay than that obtainable with a dry pan or hammer mill, the Clay Corporation of California installed a five-roller, low- side Raymond impact mill at its Lincoln plant in 1925 and since then has been economically grinding fire clay with a moisture content as high as 15 per cent. This was one of the first, if not the first, of this type of mill to be used in the grinding of clay on the Pacific coast. The pulverizer consists of a die-ring, lying in a horizontal plane, enclosed in a sheet-iron housing. A vertical shaft supports a spider from which five rolls are suspended in such a way as to always have them bearing on the die-ring. The vertical mill shaft is driven by means of beveled gear and pinion from a horizontal shaft which is connected by belt with a 60-hp. motor with suitable pulleys to give a speed of 175 r.p.m. A large fan which has a speed of 1100 r.p.m. and is belt connected to a 40-hp. motor is connected to the mill housing. The discharge end of the fan is in turn connected to a cyclone dust collector.

Jan 1, 1929

[United Engineering Trustees, Inc. W. D. B. MOTTER, JR., '40 A. L. QUENEAU, '41 ALBERT ROBERTS, '41 The Engineering Foundation GEORGE D. BARRON, '44 F. F. COLCORD, '42 A. L. QUENEAU, '41 Engineering Societies Library Board J. W. LAIST, '40 A. B. PARSONS, Ex-officio T. T. READ, '42 F. F. SHARPLESS, '41]

Jan 1, 1940

By William J. Coulter

WITHIN the past thirty years the United States has been involved in two tragic, vicious, and costly world wars. To make the world safe for democracy was the reason given for our participation, but the confusion and misunderstanding that prevails all over the world today suggests that war is not the proper approach to the attainment of that utopia. These conflicts were conceived and prosecuted by nations far advanced in civilization and culture. Their best manhood was sacrificed, a staggering tax burden was saddled on their peoples, huge financial losses were incurred, destruction of property was appalling, and cultural and peaceful scientific advancement received a setback that may require centuries to retrieve. Therefore, some basis is established for the conclusion that progress in the past fifty years has been most outstanding in the development of instruments used for death and destruction, and that progress in this direction between the two World Wars would indicate that the next war will go far toward total destruction of world civilization.

Jan 1, 1946

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By Albert Sauveur

(Winces-Barre Meeting, June, 1911.) THE instrument about to be described meets so perfectly the special needs of the metal microscopist that there seems to be little doubt but its merits must be readily appreciated by those who have had any experience in the microscopical examination of metals. The Microscope-Stand.-The microscope-stand proper, Fig. 1, consists of a microscope-tube, provided with both coarse and fine adjustments of the best construction, and with a draw-tube, rigidly mounted on a bar supported at both ends on substantial and firm cast-iron legs. The height between the table and the under side of the supporting bar is 5 in. and the distance between the supporting legs 12 inches. This arrangement' affords free space below the objective for the examination of large specimens of metals, such as full rail-sections, without detracting in the least from the value of the instrument when applied to the examination of the usual small specimen, as explained later. Many metal microscopists frequently have to examine bulky specimens, and this is altogether impossible with the ordinary microscopes as well as with the special metallurgical microscopes which have been designed and described from time to time. Recourse must be had to all sorts of makeshifts for the proper support of large specimens, or, more often, the microscopist gives up the attempt altogether, or else resigns himself to the cutting of the bulky samples into small pieces to -be laboriously polished and separately examined. It is believed that an instrument permitting the examination of large as well as of small specimens with equal ease and accu-

Dec 1, 1911

T. H Aldrich '96 Walter H. Aldridge '89 R M. Atrater, Jr '97 James B Bailey '00 Samuel Barker, Jr. '00 John F Berry '93 Charles A Bohn '93 H. A Brassert '99 Victor B. Buck '98 Frederick Burbidge '87 Frederick P Burrall '97 John Cabot, Jr '99 William McC. Cameron '97 W Gaston Caperton '94 Norman Carmichael '99 Alvin B. Carpenter '97 Charles A Chase '00

Jan 1, 1952

By R. G. Robins, O. J. Kwok

The application of chemical thermodynamic theory to high temperature aqueous systems is discussed as a basis for the explanation of thermal precipitation. The derivation of high temperature potential/ pH diagrams is briefly outlined in order to show a temperature/pH relationship for hydrolytic precipitation, which is an effect that is caused simply by heating an aqueous solution. Various examples of thermal precipitation are given, with particular reference to separation of metal values from leach solutions. Metal sulphate solutions are shown to precipitate basic sulphates, hydrated sulphates , oxides, hydroxides, and oxydroxides of the metal depending largely on the pH, the concentration of metal ion, and the concentration of sulphate or bisulphate. The CuS04-H2S04-H20 system is treated in some detail, and the separation of copper from other metal ions is investigated. Other separations involving Fe, Ni, Zn, Cd, and Cr are considered. Other advantages of thermal precipitation, such as the formation of high purity, large particle size and easily filterable materials, are presented. The kinetics of thermal precipitation are also briefly examined.

Jan 1, 1973

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

air-lift and equipped with tapered tubing of proper design, we would have a gas input consumption of about 2500 cu. ft. per bbl., which at 3 to 4c. per 1000 cu. ft. would be 7 1/2 to l0c, per bbl., and there would be very infrequent loss of production due to stoppages. It has been demonstrated that with efficient design of air-gas lift, the production of wells can be increased much beyond that obtained with the former type of air-lift employed; also that small wells can be operated by air-lift with tapered tubing at a cost that places this method in competition with beam pumps in many fields. The next step in conservation that the writer expects to have an opportunity to demonstrate is that of restoring the pressure in a pool and producing by air-gas lift all of the oil possible to lift economically. This combined operation is probably the method toward which we shall eventually be working in recovering the maximum quantity of oil from pools where the oil is recovered through bore holes. General Discussion on the Air-gas Lift H. P. Porter, Tulsa, 0kla.—The papers presented at this meeting contain a great amount of valuable information. Wonderful progress has been shown in the development of air and gas-lifts. There has been nearly everything brought out that touches upon the subject. The real point that is lacking is exact knowledge of the velocity with in the flow column which will produce the best effect—that is the thing we must know more about. Velocity in Gas-lift Flow In other lines of industry the matter of velocity of fluids in pipe lines has been well analyzed and there are known laws by which to calculate velocity of flow; for instance, in irrigation work large pumps are designed with intake pipos to employ an intake velocity of 4 ft. per scc. By reduced cross-sect'ion the velocity is increased rapidly as it enters the pump and the discharge rate is at 12 ft. per src., which in turn is reduced in the discharge column to 4 ft. per sec. Crushed coal, grain and granular material is found to be best conveyed by air when a pneumatic conveyor is employed at 100 ft. per sec. As in the design of a pumping plant or a pneumatic conveyor, the velocity at the lower end of the column in the flowing well must be controlled within certain limits for best results. Mr. Griswold, I believe, stated that they had velocity as low as 15 it. per scc. and from that up to 78 ft. per sec. Mr. Pierce and Mr. Lewis showed an ideal flow column showing how the velocity increased as the fluid was carried up the column, hut did not give any figures as to the velocity. It would be well to take that sort of a diagram to establish an ideal velocity at the lower or intake end, and then calculate the velocity from expansion of the gas as it goes up. It may be that the, ideal intake velocity would vary, depending on the depth of the well, the quantity of liquid to be handled or the pressure which it may be desired to hold. The subject is one that might be worth much research.

Jan 1, 1928

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By E. I. Larsen, E. F. Swazy, F. R. Hensel

Experience has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. Test MAteriaIs Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It mas found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended On the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as One eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from goo°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal com-position was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical propertties and certain bearing properties of this alloy are described in the present paper Preparation of Compacts Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition~ 25 per cent nickel; 7 silicon; 3 phosphorus 64 copper. This alloy is brittle in the cast condition and can be readily powdered. Sintering Procedure The blended powders were pressed at '5 to 40 tons per sq' in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By G. Y. Chin, A. R. Von Neida

The relationship between crystalline texture and magnetic anisotropy in a Co-10 pct Fe alloy has been investigated by means of X-ray pole .figures, hysteresis-loop tracings, and magnetic-torque measurements. The cold-rolled texture of a sample after 95 pct thickness reduction is of the "brass-type", that is, (110)[112/. At 500°C the cold-rolled material recrystallizes fo a (311)[112] orientation, plus a minor (210) [001] component. This texture persists up to 1400°C, at which point it is replaced by a secondary recrystallization texture, (111)[112]. Magnetic-torque measurements show that the easy axis of magnetization lies along the transverse direction in the cold-rolled material and changes to the rolling direction after primary recrystallization. This change is also reflected in the hysteresis characteristic; whereas the B-H loop along the rolling direction is nonsqunre with a low value of residual induction (750 vs 19,000 gauss at saturation) for the cold-rolled material, the annealed sample exhibits a very square loop with a large value of residual induction (16,000 gauss). Theoretical torque curves calculated from the texture data on the basis of magnetocystalline anisotropy energy compare favorably with the observed torque curves. Values of the crystal anisotropy constant, K1, obbained from these comparisons are in good quantitative agreement with single-crystal data. Furthermore, both the torque amplitude of the poly crystalline material and the magnitude of K1 obtained with a single crystal show an identical temperature dependence over the range from —195° 10 +220°C. It is thus conclzided that the magnetocrystalline anisotrpopy erlergy is chiefly I-esponsible. for the nzagnetic allisotropy of textured Co-10 pct Fe alloy. THE results of a study on the relationship between crystalline texture and magnetic anisotropy of an alloy containing 90 pct Co and 10 pct Fe by weight are reported in this paper. The alloy has an fcc structure: a saturation magnetization of about 19,000 gauss,2 and a nearly zero value of magnetoatriction.3 puzey4 has reported a large crystalline anisotropy constant of -7.4 X 105 ergs per cu cm, indicating the (111) directions as the easy axes of magnetization. Hence, texture variations resulting from cold work and annealing are expected to introduce a magnetic anisotropy in the polycrystalline material through the alignment of these (111) easy directions. In the present study, magnetic anisotropy of both rolled and annealed strips was determined by magnetic-torque measurements and hysteresis-loop tracings The results were correlated quantitatively with calculations based on texture data obtained by the X-ray pole-figure technique. It is established that the magnetocrystalline anisotropy energy is indeed chiefly responsible for the magnetic anisotropy of textured Co-10 pct Fe alloy. EXPERIMENTAL Material Preparation. The alloy nominally contained 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn by weight, the chief impurities being nickel, carbon, and silicon (less than 0.5 pct total). The cast ingot was rolled to strips 10 mils thick and slit to 1 in. in width. After strand annealing at 900°C in a hydrogen atmosphere, these strips were further cold-rolled to various thicknesses down to 0.25 mil (97.5 pct reduction), with samples collected for study of the development of texture and magnetic anisotropy as a function of thickness reduction. subsequently, samples cold-rolled from 100 mils to 0.25 mil were obtained, thus extending the thickness reduction range to 99.75 pct. In addition, 0.5-mil samples cold-rolled from 10 mils were selected

Jan 1, 1965