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By C. C. Harris Discussion by B. K. Loveday

B. K. Loveday (National Institute for Metallurgy, Johannesburg, Republic of South Africa) - The paper and subsequent technical note' describing a method of determining the parameters of the three-parameter size-distribution equation developed in the paper were read with much interest. This equation was also used at National Institute for Metallurgy (NIM) to describe size distributions in grinding tests, because it was necessary to have a single equation to describe the size distribution at any time during a test. A graphical method also was used to determine the three parameters, and the use of this method as an alternative to Professor Harris's latest method is discussed here. The three-parameter model can be expressed as follows: Eq. 1 can be rearranged and transformed to Yield a linear reiationship between Y and X (transformed) log

Jan 1, 1970

By Renato G. Bautista, KNona C. Liddell

A model of the reaction of chalcopyrite, CuFeS2, with Fe3+ and with 02 is considered. Homogeneous solution phase reactions are assumed to be always at equilibrium throughout the dissolution of the mineral. The dissociation of USOb- and several complexation reactions involving cu2+, Fez+ and Fe3+ are incorporated in the model equations. The relative importance of Fe3+, 02, and H+ as oxidants and the role of solution equilibria are assessed and the implications for leaching practice discussed.

Jan 1, 1981

By A. U. Seybolt, R. L. Fullman

THE Hume-Rothery rule relating the relative sizes of the solvent and solute atoms in a substitutional solid solution for moderate to extensive solubility is, of course, well known and much used in the design of alloys. No such rule has been obtained for interstitial solid solutions, although a qualitatively similar relationship would be expected. Among the most common interstitial elements, oxygen, carbon, and nitrogen which can dissolve in important amounts in the transition metals, only in the case of oxygen is there enough solubility data available for an examination of the possibilities of a simple relationship between the extent of solubility and the properties of the metal solvents. Three properties were examined: 1—size of the octahedral space V into which oxygen atoms fit, 2— the elastic modulus E, and 3—the free energy ?F of formation of a low oxide, such as is known to be, or would be expected to be, in equilibrium with the terminal solid solution. The size factor or octahedral volume is so closely associated with the well known Hume-Rothery con- cept of size factor that additional development of this subject is hardly necessary. The octahedral volume used was not corrected to an elevated temperature, as this correction would have made no significant difference. The second factor, Young's modulus E, must be considered, since it is a measure of the strain energy required to force neighboring atoms apart so that an oxygen atom may enter the octahedral volume. The temperature dependence of the elastic modulus of many metals has been reported by Köster,1 but for a rather limited temperature range. Since the

Jan 1, 1955

By F. W. Aul, R. C. Glenn

EXTRACTION techniques are of particular importance in determining size, shape an: crystal structure of particles smaller than l000Å in steels and other alloys. However, artifacts that can arise during the preparation of extraction replicas may lead to erroneous conclusions. The purpose of this note is to illustrate some of these artifacts and the misinformation that can result from their presence. An alloy of iron with 0.8 pct Cu was investigated in the following conditions: 1) Solution treated 3 days at 925°C in dry hydrogen and quenched in water. Aged in steps to precipitate copper, as follows: heated to 700°C, held 1 day; then furnace cooled to 50O°C, held 3 days; then furnace cooled to room temperature. 2) Solution treated 3 days at 925OC in dry hydrogen and furnace cooled to room temperature. 3) Solution treated 3 days at 925OC or 17 hr at 1100°C in dry hydrogen to dissolve all copper, then quenched in water. A normal parlodion dry-extraction technique was employed after etching the specimens with super picralP or with 2 pct nital. A wet-extraction method

Jan 1, 1962

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported' only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.' Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C'u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By William Greenawalt

The Greenawalt electrolytic copper extraction process is applicable to suitable oxide ores, sulfide ores and concentrates, and low-grade matte. The process is self-sustaining in acid on sulfide ores or concentrates, on mixed ores, on high-grade oxidized ores; and on low-grade oxidized ores the amount of acid to be purchased or manufactured is greatly reduced. The ferric iron is under easy control, and copper may be effectively deposited from solutions of any acid or iron content likely to be used in copper leaching. From 60 to 75 per cent. of the copper may be removed from the solution in passing through the electrolytic department, before returning the solution to the ore. The amount of copper requiring chemical precipitation, from the waste and foul solutions, is only about 5.0 per cent, of the total copper produced, and this 5.0 per cent. is converted into the electrolytic metal in the regular operation of the process. The entire process can be made practically automatic, and can be carried out mechanically. There is no uncertain departure of any kind in the application of the process; no unusual or unproved apparatus is used. EVER since electrolytic copper refining gave promise of success, about a half century ago, efforts have been made to apply the idea to the extraction of copper from its ores. The methods of attack have, usually, been to leach with a dilute acid and then to deposit electrolytically the copper from the resulting solution with the simultaneous regeneration of the solvent used in the process. Many efforts have been made, and many patents have been taken out, both in the United States and abroad, to give this idea practical application, but only within the past few years have the difficulties been surmounted. Leaching and electrolysis, as applied to copper ores, are among the most promising fields in modern metallurgy. New conditions are arising, which will bring the wet methods into prominence; while high freight rates and increasing cost of fuel will tend to limit smelting to highly favored localities. The possibilities offered by the installation of hydro-electric plants and the greatly enlarged range of power transmission will greatly widen the field of electrolytic methods.

Jan 1, 1924

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By J. E. Campbell, A. W. Wesner, M. Pobereskin

This paper summarizes the results of an investigation sponsored by The Coates Steel Products Company. The objective was to determine the relative effects of certain chemical and physical properties on the wear resistance of grinding balls when grinding cement. In making this study, a number of types of balls were used in both dry and wet grinding in commercial ball mills. The radioactive-tracer technique was used in separating the test balls from the rest of the mill charge and in sorting the different types of halls that were all tested at the same time for each of the grinding operations. PROCESSING OF GRINDING BALLS In order to determine whether the properties of grinding balls, namely, composition, microstructure and hardness, can be related to the rate of wear, the halls used in this study were selected to represent various combinations of these properties. It was recognized that the mechanism of wear was not the same in the wet mill as in the dry mill. Therefore, the types of balls tested in each of the two environments were not necessarily the same. However, all of the types of balls evaluated in the dry mill were tested simultaneously for one time period, while those evaluated in the wet mill were tested simultaneously for three different time periods. All of the test balls were separated from the charge when the mill was dumped. All of the balls were of 0.940-inch diameter when charged, and all but the regular production balls were finish ground to this size to eliminate the decarburized surface layers. The steels and processing methods used, as well as the micro-structures and hardness levels of the balls, are described as follows: Regular production forged SAE 1095 steel balls were used in both the wet and dry mills. They were forged to a nominal diameter of 0.940 inch and quenched in oil from the forging temperature. Each retained a partially decarburized surface layer from the forging bar stock; the maximum depth of this layer was about 0.030 inch and the decarburization was negligible where the ball was sheared from the bar. The hardness at the surface was 40 to 46 Rock-well C in the partially decarburized area and 57 to 62 Rockwell C in the areas not decarburized. The hardened zone extended to a depth of about one-third of the radius. Below the decarburized layer, the hardened zone consisted primarily of hard as-quenched martensite with varying amounts of retained austenite. This structure changed to fine pearlite at a depth of about one-third of the radius. In order to eliminate the effect of the decarburized layer, a set of production balls of SAE 1095 steel was forged to about a 1-inch diameter, quenched in oil from the forging temperature, and ground on ball-bearing grinding equipment to a 0.940-inch diameter to remove the decarburized layer. The balls' hardened zones were similar to those in the previous set. The hardness of the finished surfaces was 52 to 60 Rockwell C. A slight amount of decarburization apparently remained after the removal of about 0.030 inch from the surface. Balls of this type were tested in the dry mill only. Another set of forged SAE 1095 steel balls of 1-inch diameter was heated to 1500 F and quenched

Jan 1, 1961

By R. A. Wattenbarger, H. J. Ramey

The trend in gas well testing has been to rely more on the early-time flow data of drawdown and buildup tests than on stabilized flow tests. The stabilized testing methods often are not adequate for complicated modern gas reservoirs because many of these reservoirs have extremely low permeabilities and the transient flow period of a well test can last for days or weeks. It has become common to augment the flow capacity of gas wells by hydraulically fracturing their producing formations. In deep reservoirs the induced fractures are generally vertical and tend to follow a single plane of weakness. The presence of a vertical fracture at the wellbore complicates the transient flow behavior of a low permeability gas well. The flow is further complicated when turbulence occurs near the wellbore. Russell and Truittl published transient drawdown solutions for vertically-fractured liquid wells. They developed methods of drawdown and buildup testing utilizing these solutions, which were based on numerical simulation. Clark2 applied the basic Russell-Truitt solutions to analyze fractured water injection wells by falloff tests. Field examples were given to substantiate the method of analysis. The Russell-Truitt solutions and well testing methods can be extended to gas well flow. Millheim and Cichowicz3 presented the drawdown equations for *Now with Scientific Software Corp., Denver. ideal gas flow, including the effects of formation damage and turbulence. Two actual field cases were presented, both of which exhibited extensive fractures and turbulent flow. For the pressure range of these well tests, the use of ideal gas equations was acceptable. These field cases were significant in being the first published data showing the occurrence of turbulence in fractured gas wells. We, also, observed such cases in practice. Our purpose here is to extend the theory of fractured gas well testing to the flow of real gases. To determine the effects of wellbore storage and turbulence on well test interpretation, we developed a finite-difference model to simulate well test conditions. Since gas wells usually are widely spaced and have high compressibility, the emphasis has been put on the early transient behavior before the effects of the outer boundary are noticeable at the wellbore. The Mathematical Model The geometry of our mathematical model is similar to that used by Prats.4 The well is centered in a circular uniform reservoir. A vertical fracture of infinite flow capacity penetrates the formation and passes through the wellbore. The wellbore itself is not important. Fig. 1 shows a sketch of the problem. Fig. 2 shows the idealized model. The equation for the flow of real gas in a porous medium with uniform porosity, permeability and thickness is5-7

Jan 1, 1970

By J. N. Chew, C. A. Connally

A correlation is presented for predicting the viscosity of gas-saturated crude oils under reservoir conditions. It is based on the dead oil viscosity and the solution GOR. The correlation was developed from a study which showed that at a fixed solution GOR, the relation between the gas-saturated oil viscosities and the correrponding dead oil viscosities is a straight line on logarithmic coordinates. Data from 457 crude oil samples from the major producing areas of the U. S., Canada and South America were used. The best straight lines through the data were fitted by the method of least squares with a digital computer. The correlation is presented in the form of an equation and also in a convenient gra-phical form. INTRODUCTION The viscosity of gas-saturated crude oils under reservoir conditions is an important physical property used in reservoir engineering calculations. Many difficulties are inherent in the sampling of gas-saturated oils and in the laboratory measurement of their viscosities. Therefore, it is frequently neither possible nor convenient to obtain measured values, so the viscosity must be estimated from other, more readily available data. This paper presents a correlation for predicting the viscosity of gas-saturated crude oils. The correlation is based on the amount of gas in solution and the viscosity of the dead oil at the temperature of interest. A previous correlation of these variables was presented by Beal. In comparison, the correlation presented here extends to a higher GOR and to a lower dead oil viscosity. Over the range of variables covered by both, this correlation is based on approximately 11 times as many oil samples. DEVELOPMENT OF CORRELATION A study was made of the variables or parameters which could be used to relate the viscosity of a gas-saturated oil to its dead oil viscosity. Preference was given to those variables which are easily and commonly measured in the field or in the laboratory. It was found that either the differential liquid formation volume factor or the solution GOR of the gas-saturated oil could be used as a correlating parameter. The solution GOR was se- lected for the correlation because of its simplicity and availability. In an attempt to refine the correlation by introducing a second parameter, the following additional variables were tested: differential liquid formation volume factor at the reservoir bubble point, the formation volume factor at the saturation pressure for the GOR of interest, reservoir temperature, viscosity of C+ fraction at 100°F and atmospheric pressure, weighted average gravity of gas in solution, oil gravity, reservoir bubble point pressure, saturation pressure at the selected GOR and reservoir temperature, and gas mol fraction. None of these improved the correlation to any significant extent. It was found that at any fixed solution GOR, the relation between the gas-saturated oil viscosities and the corresponding dead oil viscosities is a straight line on logarithmic coordinates, for the range of variables investigated. This straight-line relationship was used for the correlation. Viscosity data on a total of 457 crude oil samples were used. The data were obtained with rolling ball-type viscometers. The samples came from all of the important producing areas of the U. S., as well as from Canada and South America. Their geographical distribution is shown in Table 1. The ranges of properties represented by these samples are as follows: For each crude oil sample the viscosity of the liquid phase from each step of a differential liberation was plotted against its solution GOR on semi-logarithmic paper. A smooth curve was drawn through the points and values of viscosity in centipoises were read from

By Henry N. McCarl

Mineral aggregates are those natural and manufactured industrial mineral and rock materials that provide bulk and strength in port- land cement concrete, bituminous concrete mixes, and plaster or stucco surfaces. They may also provide special characteristics such as thermal and acoustical insulation, weight, surface textures, abrasion resistance, and impermeability to various concrete products and mixes. Most aggregates are relatively inexpensive materials, but despite their low unit value, the tonnages consumed each year in the United States and throughout the world make mineral aggregates by far the leading industrial mineral and rock materials both in terms of volume (tonnage) produced and value consumed. The major use of mineral aggregates is in concrete. The low cost, high bulk aggregates tend to keep concrete construction costs at levels competitive with other building materials. Other major uses of aggregates include highway and railroad base or ballast materials, graded fill, and various industrial uses such as metallurgical and chemical fluxes and raw materials-these latter uses are often considered nonaggregate uses of mineral aggre- gate materials. The value of mineral aggregate materials at the production plant varies from less than a dollar per ton to several dollars per ton for most crushed stone and sand and gravel, $2 to $15 per ton for slag and expanded clay or shale aggregate, to as much as $60 to $100 per ton for expanded perlite or vermicu- lite. The more specialized the use, the higher the price-although there are naturally some exceptions to this rule of thumb. The first four parts of "Construction Materials" deal with the utilization of four major mineral aggregate types: Crushed Stone, Light- weight Aggregates, Sand and Gravel, and Slag. While the focus will be on the use of these industrial minerals and rocks there will also be some coverage of sources, mining and production, especially in those cases where they are

Jan 1, 1975

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,'-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By R. S. Busk

TWO groups of binary alloys were prepared. The first group consisted of those elements relatively soluble in magnesium: Li, Al, Zn, Ga, Ag, Cd, In, Sn, Hg, T1, Pb, and Bi. These are predominately Group B elements. The second group consisted of most of the remaining metallic elements, all of which are relatively insoluble in magnesium: As, Au, Ba, Ca, Ce, Cu, Ir, La, Mn, Ni, Pd, Pt, Rh, Sb, Si, Te, Ti, W, and Zr. These are all Group A, transition, or rare earth elements. Alloys of the first group were prepared by melting sublimed magnesium and elements as pure as obtainable in a graphite crucible, using a standard flux1 for protection. The melts were poured into a small graphite mold to produce 3xY4 in. diam slugs. Spectroscopic analyses were made of each slug. In all cases, the total impurity content was less than 0.05 pct. The slugs were then heat treated 5°C below the eutectic temperature until complete solution, as judged metallographically, was obtained. Filings from the center of the slugs were compacted at room temperature into 1/2 in. long x 1/4 in. diam cylinders, sealed in pyrex under 1/2 atm of purified argon, annealed at the heat-treating temperature for 1 hr, and quenched in water. After the X-ray diffraction patterns were made, each compact was analyzed chemically for the solute. It was found that the Mg-Li alloys reacted during filing to reduce the Li in solid solution. For this series of alloys, the slug was cold worked, annealed in purified argon, the surface dissolved in dilute HC1 to a depth of about 0.005 in., and the X-ray exposure made on the fresh surface. This procedure resulted in sharp, continuous lines and in true values for the lattice parameters. The alloys in the second group were prepared in the same way except that about 1 wt pct of each solute was added. Since the solubility limit was exceeded, not all the solute dissolved. These alloys were analyzed spectroscopically only to confirm the presence of the solute. The diffraction patterns were of the back-reflec-tion type using the characteristic copper radiation* and a flat cassette. Both the film and the specimen were rotated. The specimen temperature was maintained at 25" ± 1°C. The films had sharp lines; their diameters were measured directly to 0.01 cm. The parameters were calculated from the line diameters using a modified version of Cohen's extrapolation method.2 his method effectively eliminates systematic errors such as film shrinkage, inaccurate alignment, and non-precise film-to-speci-men distance. The random errors were minimized

Jan 1, 1951

By Mark J. Klein

An internal-friction profile induced by nitrogen in Cr-35 at. pet Re was studied as a function of nitrogen concentration and heat treatment. From these studies, the solubility of nitrogen in this alloy was deduced. The equilibrium solubility of nitrogen in chromium does not appear to be substantially changed by the addition of 35 at. pet Re to chromium. However the precipitation kinetics of nitrogen from solution are significantly decreased. IT has been found that rhenium has a beneficial effect on the low-temperature ductility of Group VI-A metals. As part of a study to investigate the mechanism of this increased ductility, it was of interest to compare the concentration of interstitials retained in solution in one of these ductile bee alloys with the concentration retained in solution in its base metal. In this regard, a study of the solubility of nitrogen in ductile Cr-35 at. pet Re was selected for this phase of the investigation because the solubility of nitrogen in the base metal, chromium, has been determined over a fairly large temperature span.1-3 In addition, nitrogen is known to have an embrittling effect on chromium,4 but does not appear to have a comparable embrittling effect on Cr-35 at. pet Re.5 The experimental method selected for this study was the measurement of internal friction. This technique allows interstitial-concentration measurements to be made in bee metals that are sensitive to small changes in the concentration of a particular interstitial, even when other interstitials are present. When subjected to a cyclic stress, interstitial atoms in solid solution give rise to an internal-friction peak whose origin is the stress-induced ordering of interstitials into preferred lat- tice sites. These internal-friction peaks signify a dissipation of elastic energy which is greatest when the period of oscillation is comparable with the relaxation time for the attainment of an equilibrium interstitial distribution. For dilute interstitial binary alloys, the height of the internal-friction peak is proportional to the concentration of interstitial atoms in solid solutions. snoek8 has shown that the internal friction, Q-1, may be expressed by the equation where A is the relaxation strength, ? is the angular frequency, and 7 is the relaxation time. The relaxation strength, A, is proportional to the concentration of interstitials taking part in the relaxation if no interaction occurs between solute atoms. Thus values of peak height, which can be determined as a function of temperature, give a measure of the relative concentration of interstitial atoms in solution at various temperatures. If equilibrium has been attained, the peak heights will be proportional to the interstitial solubilities. The constant that relates A to the interstitial concentration can be determined experimentally from peak-height measurements as a function of concentration for specimens of constant crystallographic orientation. When this has been done, Q-1 measurements can be used to determine solubilities according to the equation C - KQ-1 where C is the soluble interstitial concentration and K is a constant that can be experimentally determined. It is possible, however, that lattice imperfections may bind interstitials to certain lattice sites. Internal friction does not measure these interstitial~, but does measure interstitials which are free to move in the normal lattice sites when subjected to an applied oscillating stress. On alloying the pure metal with a substitutional

Jan 1, 1965

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

By R. J. Jackson, D. E. Williams, W. L. Larsen

The phase diagram of the Ta-Zr system is presented with a discussion of the methods used in its determination. The solidus contains a minimum at 1820°C near 25 wt pet Ta. A complete solid solution exists at elevated temperatures between tantalum and ß zirconium. This solid solution decomposes monotectoidally at 800°C and 12 wt pet Ta. The maximum solubility of tantalum in a zirconium is slightly less than 2 wt pet, and decreases with decreasing temperature. The solubility of zirconium in tantalum is 5 wt pet at the monotectoid temperature and about 2 wt pet at room temperature. THIS investigation was part of a program of research on refractory metal alloy systems having potential application in nuclear reactor technology. Preliminary prop-ess has been reported in the Ames Laboratory annual research reports.l Most of the previously reported work on the Ta-Zr alloy system consisted of partial phase diagram investigations and the determination of the mechanical properties of the zirconium-rich alloys. Anderson eta1.2 studied alloys containing up to 30 wt pet Ta as part of an investigation of several zirconium alloy systems. These investigators also determined some of the mechanical properties of the alloys at room temperature and 650°C. In a discussion of Anderson's work, Pfei13 suggested that the bright phase in the microstructures of the intermediate alloys is a tantalum-rich solid solution or an intermediate phase in a matrix of ß zirconium solid solution. Litton,4 Keeler,5 and Chubb6 determined the mechanical properties of zirconium-rich alloys at ambient and elevated temperatures. Van Thyne and McPherson7 reported the tensile properties

Jan 1, 1962

By Shiou-Chuan Sun

SHIOU-CHUAN SUN (author's reply).-Thanks are extended to Professor Hassialis for his recognition of the usefulness of a new tool, the cataphoretic cell, as an adjunct to the bubble machine and the abstraction test. His questions concerning adsorption, dielectric constant, floatability, activation, and depression are interesting and worthy of discussion. I According to Mueller,28 it is questionable that any of the present formulas gives absolute values of zeta potentials which are completely accurate. The problem is further complicated by the question" of whether the "dielectric constant" has any meaning at all for such a microscopically thin layer. With these in mind, the results in this paper should be considered in the relative sense as a first approximation and not as absolute quantities. Adsorption Referring to item a of Fig. 8, the dielectric constant and the viscosity of the xanthate solutions are the same for galena, sphalerite and quartz. If dielectric constant and viscosity (but not the adsorption) were the first-order variable of the cataphoretic system, as claimed by Professor Hassialis, then the magnitudes of zeta coefficient of galena, spha)erite and quartz would have been similar to each other. These are not. The big difference of zeta coefficient of these three minerals in the same xanthate solutions is not altogether unjustified to be attributed to their difference in adsorption of xanthate ions. This is supported by the results of chemical abstraction tests reported by Ince.14 Again, the big difference of zeta coefficient between wollastonite, calcite, and fluorite in the same laurylamine hydrochloride solutions (p. 118, Figs. 58, 59, and 60 of ref. r5) also indicates that the cataphoretic system is not governed chiefly by the dielectric constant. Beside the data shown in Fig. 8, other experimental evidences15 which support the idea of correlation between adsorption and zeta coefficient are: (I) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of various concentrations of sodium cyanide, (2) there is a qualitative parallelism between the zeta coefficient curve and the chemical abstraction curve of sphalerite in solutions of constant concentration of copper sulphate at different pH values, and (3) there is a qualitative parallelism between zeta coefficient curve and chemical abstraction curve of quartz in solutions with constant concentration of barium chloride at different pH values. The above mentioned experimental results are generally in agreement with Gouy's double layer theory,1-5 and support this idea that the concentration and the kind of ions adsorbed at the mineral surface and in the adjacent surrounding liquid chiefly govern the electrokinetic phenomena. Dielectric constant and viscosity of the liquid medium may be of somewhat lesser importance. It follows that the correlation between the coefficient and adsorption as claimed in this paper is justified. Dielectric Constant The term "dielectric constant " was first introduced into the electrokinetic equations by Perrin.30 In a footnote of his publication he states that Holmheltz has forgotten to include the dielectric constant. The conversion of the moment29 to the zeta potential involves an additional difficulty and confusion not involved for the moment, namely, assigning a value to the dielectric coefficient. This is conventionally assumed to be constant and equal to the dielectric constant of the bulk liquid. 21 The published literature 10, 12 indicates that the values of dielectric constant for dilute chemical solutions have been assumed as those of pure water.

Jan 1, 1947

By R. S. Olson

An analysis of the wash thickener-two stage filtration circuit was undertaken to quantitatively describe the circuit performance. On the basis of information developed in this study, the factors of major importance in reducing soluble loss are: filter wash, wash zone size, filter capacity, filter feed pulp dilution, blow back, filter cloth, water to repulp, water to primary wash, water to feed pulp and thickener underflow. The wash thickener-two stage filtration circuit has been used in many hydrometallurgical plants to separate solute from leach solids. As many as 20 to 30 plant operating variables determine the performance of the wash circuit and hence the soluble loss. The complex relationships of these variables, with each other and with soluble loss, make the evaluation of their effect on mill performance difficult. An analysis of this type of circuit was undertaken to quantitatively describe the circuit performance. THE CIRCUIT The diagram in Fig. 1 represents the operation of the wash thickener-two stage filter circuit. This circuit provides for counter current, cross current or for a combination of countercurrent-cross current operation. The feed pulp stream, J, is intended to include any solution or water, other than primary and secondary filtrate, which enters the wash thickener. Except for filter washing, the operations in the circuit are simple mixing operations which can be described by material balance. The concentration of solute in the filtrate and cake solution after application of wash liquor cannot be described by simple material balance. The displacement washing equation, derived by Rhodes1 and extended by Choundhury and Dahlstrom,2 appears to best describe this case of miscible displacement in porous media. In a useful form, it is

Jan 1, 1963

By George J. Bancroft

AT the New York meeting of the Institute, April, 1907, I presented a paper entitled, The Formation and Enrichment of Ore-Bearing Veins,1 in which paper I advanced the following propositions (1) That the majority of mineralized veins are the product of expiring vulcanism ; (2) that most of these veins were primarily mineralized by comparatively rich solutions in comparatively short periods of time; (3) that the solutions gained their metal-values from a comparatively rich source; (4) that there is a barysphere containing large amounts of the useful metals; (5) that eruptions spring from various depths and bring various kinds of magmas towards the surface; and (6) that only those eruptions which disturb the barysphere and bring a magma rich in metals sufficiently near the surface to be leached by vein-making solutions are productive of valuable ore-deposits, other eruptions producing barren veins. Ore-deposits due to magmatic segregation were not included in this general survey. As a result of considerable further study I have modified my views in some respects, while in others I feel more sure than ever of the ground taken at that time. That ore-bodies are infrequent occurrences and born of extraordinary conditions I think is now generally accepted. The theory that persisted for a time-namely, that ore-bodies were formed by the ordinary ground-water, which consists of extremely dilute solutions, derived from leaching extremely lean surface-rocks, and which must occupy enormously long periods of time in concentrating the values so leached, is, I think, now pretty generally regarded as not applicable to the great majority

Jan 1, 1913

By George J. Bancroft

At the New York meeting of the Institute, April, 1907, I presented a paper entitled, The Formation and Enrichment of Ore-Bearing Veins,' in which paper I advanced the following propositions: (1) That the majority of mineralized veins are the product of expiring vulcanism; (2) that most of these veins were primarily mineralized by comparatively rich solutions in comparatively short periods of time; (3) that the solutions gained their metal-values from a comparatively rich source; (4) that there is a bary-sphere containing large amounts of the useful metals; (5) that eruptions spring from various depths and bring various kinds of magmas towards the surface; and (6) that only those eruptions which disturb the barysphere and bring a magma rich in metals sufficiently near the surface to be leached by vein-making solutions are productive of valuable ore-deposits, other eruptions producing barren veins. Ore-deposits due to magmatic segregation were not included in this general survey. As a result of considerable further study I have modified my views in some respects, while in others I feel more sure than ever of the ground taken at that time. That ore-bodies are infrequent occurrences and born of extraordinary conditions I think is now generally accepted. The theory that persisted for a time—namely, that ore-bodies were formed by the ordinary ground-water, which consists of extremely dilute solutions, derived from leaching extremely lean surface-rocks, and which must occupy enormously long periods of time in concentrating the values so leached, is, I think, now pretty generally regarded as not applicable to the great majority

Jan 1, 1910