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By W. A. Tiller, W. C. Johnston

A theoretical analysis of alloy solidification in which the effective partition coefficient, k, of the solute is allowed to vary as a function of interface position is performed. A variety of solute distm'butions in the solid is predicted depending upon the functional dependence of k with interface position. Conversely, the variation of k with interface position required to produce a particular solute distributzon in the solid can be calculated. These preciictions have been tested by controlling the width of the momentum boundary layer in the liquid as a function of interface position with a rotating mugnetic field. One of the objects of controlled solidification is to utilize the freezing process for the preparation of crystals of specific materials containing a predetermined distribution of solutes. For example, a thermoelectric power generation material may exhibit a figure of merit, 2,' as a function of temperature, T, and solute concentration, C, as illustrated in Fig. 1. If we wish to use this material in a device between the temperature limits T1 to T2 a significantly greater efficiency will result from the device if the thermoelectric element illustrated in Fig. 1 consists of a range of solute concentrations appropriately located with respect to the temperature distribution rather than using a sample of constant solute concentration. For this reason and many others2 we are interested in programming and controlling the solute distribution in a single crystal

Jan 1, 1962

By Leo Brewer, Gerd M. Rosenblatt

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At

Jan 1, 1962

By J. E. Flinn, E. R. Gilbert

Recently, Green reported some high-temperature, 0.60 to 0.89 T3, creep results on unalloyed tantalum. From his study he determined an activation energy of 114 kcal per mole for steady-state creep using the T, differential-temperature method25 for testing. He accounted for the difference between this value and 110 kcal per mole for self-diffusion by the temperature dependence of the elastic modulus, 4 kcal per mole. This reported activation energy is in apparent disagreement with that which can be determined from Green's isothermal data, which we have plotted as log creep rate vs 1/T in Fig. 15. From this figure, it appears that there are two activation energies of -185 kcal per mole at the higher temperatures and -75 kcal per mole at the lower temperatures. It is not obvious that the data can be fitted to a straight line corresponding to an activation energy of 114 kcal per mole. One is led to two possible conclusions regarding Green's study: there are two discrete processes controlling the creep rate from 0.60 to 0.89 Tm or the apparent activation energy is not discrete but continuously increases with increasing temperature. The former speculation would be in closer agreement with the high-temperature creep behavior of tungsten.28 The apparent disagreement between the activation energies determined by the AT and isothermal methods certainly suggests that further study on the high-temperature creep of tantalum is needed.

Jan 1, 1967

By Eugene C. Robertson

INTRODUCTION A direct proportionality between the observed displacement of a fault and its thickness of breccia and gouge has been proposed recently (Robertson, in press). To validate this finding, an explanation of the mechanics of continuous breccia formation is needed and is offered in this paper. A summary of evidence for the finding will show why an explanation is needed. The correlation between fault displacement [d] and accompanying breccia- plus-gouge thickness [t] seems to be linear and reasonably well established over 6 orders of magnitude, with a range in [d] from 1 mm to 1 km, on a trend of [d/t]= 100, shown in Figure 1. Most of the points are for faults observed underground in mines. The [d] – [t] relation is limited to normal and reverse faults, that have a flat to steep dip and a displacement less than 5 km. It is not applied to large strike-slip and low-angle overthrust faults, whose displacements and breccia thicknesses are widely variable and uncertain. Undisplaced jointed rock is not included in the thickness measurement. A complete description of sources and analysis of the data is given in Robertson (in press). One would intuitively expect that continued movement on a fault would grind up the previously formed breccia and gouge and not produce any more, but the evidence (Fig. 1) indicates otherwise. A physical model to explain continuous formation of gouge and breccia from the wall rocks can be obtained from laboratory experiments on friction.

Jan 1, 1982

By E. A. von Hahn, T. R. lngraham

Cementation rates ulere studied by rotating an elec-tropolished or etched copper strip in aqueous solutions, of either perchloric acid or alkaline cyanide, containing silver ions. The rates of cementation were more rapid in acidic media than in cyanide media. In both, the rates varied with the rate of rotation of the copper strip. The deposits formed in the acidic solutions were finely divided, loosely adhering powders. Those formed in the cyanide solutions were dense and adherent. The presence of the deposits influenced the cementation rates. In the acidic solutions the rate was enhanced, possibly because of the increased cathodic area. In the alkaline solutions the rates were decreased in the presence of the deposits. This has been attributed to restricting the diffusion of the copper ion from the rnetal outward into the bulk of the solution. In an earlier paper1 the authors described a kinetic study of the cementation of palladium on copper in perchloric acid solutions. That work indicated that there were two stages in the palladium cementation process. The first, more rapid stage was consistent with rate control by the diffusion of Pd11 ions to the copper surface and/or by chemical reaction at the surface. The second stage was consistent with rate control by the diffusion of copper ions from the copper surface, through the deposit, out into the main body of solution. The effect of the type of deposit on the rate of cementation is of particular interest because it may be one of the primary features involved when large quantities of metal are to be cemented from solution. No substantial investigations of the effect seem to have been made. Accordingly, an extension of the previous work was arranged to study the cementation of silver on copper. This system was selected because of the convenience of the analytical methods, the previously established technology with copper, and the fact that the system could be studied in both acidic and alkaline media. By selecting perchloric acid and alkaline cyanide solutions as the media, it was hoped that some assessment might be made of the effects, on cementation, of having the silver ion present in a virtually uncomplexed state and in a highly complexed state. EXPERIMENTAL The cementation rates were studied, as previously described,' by rotating a copper strip (1.0 by 23.2 cm) clamped to the peripheral surface of a lucite cylinder. The solutions were kept at constant temperatures (±0.05°C) under an atmosphere of purified nitrogen, and samples were taken periodically for analysis. The initial solution volume was 1000 ml and the sample volume 5 ml. The initial silver(1) ion concentrations were made low (0.5 to 1.0 x 10-4 moles per liter) to minimize the influence of the cemented deposit on rates. The solutions were prepared by dilution of suitable aliquots of silver perchlorate and silver cyanide stock solutions. Both stock solutions were prepared from purified silver powder (Johnson, Matthey, and Mallory Ltd.) with redistilled deoxygenated water, and they were kept under an atmosphere of purified nitrogen. To prepare the stock solutions, weighed amounts of silver powder were dissolved with nitric acid. For the AgC104 stock solution the silver nitrate solution was evaporated twice to near dryness with perchloric acid and then made up to volume: For the NaAg(cN)2 stock solution, the silver ions were precipitated with sodium hydroxide solution. The precipitate was filtered, washed thoroughly with redistilled water, dissolved with 1.1 times the required stoichiometric amount of sodium cyanide solution, and made up to volume. The small amounts of free perchloric acid and sodium cyanide present in the stock solutions were disregarded in the preparation of the solutions. The copper strips were cut accurately from 0.025-in. sheet (American Metal Climax OFHC brand) and annealed for 1.5 hr at 470°C in a stream of nitrogen. Analyses of the solution samples for silver and copper were done with a Techtron Model AA-3 atomic absorption spectrophotometer. Calibration standards of the same composition as the experimental solutions were prepared and analyzed simultaneously with the samples. No difficulty was experienced in the analyses, and the reproducibility was within 1 to 2 pct in both alkaline cyanide and perchloric acid solutions.

Jan 1, 1968

By AIME AIME

AT a joint meeting of the Tulsa Geological Society and the Mid-Continent Section of the A; I. M. E., held at Tulsa on March 21, the history of unit development in the Kettle- man Hills field was discussed. Robert C. Patterson? Super- visor for the U. S. Geological Survey at Taft, Calif., was the speaker. An abstract of some of his remarks follows: On July 1, 1923, curtailment agreement for two years was made between the operators of North Dome Kettleman and the U. S. Department of the Interior. In this it was agreed to consider a plan of unit development, or other cooperate method of developing the structure. As a result, Kettleman North Dome Association was incorporated in December, 1930, as a non-profit cooperative corporation under the laws of California. Approved in January, 1931, by California Oil and Gas Supervisor and by Secretary of Interior. On Feb. 10, 1931, it became an active organization through election of executive officers and eleven- directors. General manager chosen. Association started to function April 1, 1931. Assumed control of 10,800 acres of proved and semi-proved land, as shown in Table 1.

Jan 1, 1932

By R. T. Webber, R. B. Owen

The vapor phase deposition of molybdenum and tungsten from the hexacar-bonyls has been thoroughly investigated by Lander and Germerl, and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2'3 could be similarly deposited, but did not investigate this metal extensively. Recently, conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. Apparatus and Technique The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T² and T3 containing crystals of the carbonyl. T² is kept in a constant temperature bath (not shown), while T³ is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Se, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by Sb is used to determine the volume included by S4, S6, SB, Slot the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: (I) the specimen temperature, from room temperature to about 1000°C, (2) the carbonyl vapor pressure, from 40 to 220 microns, and (3) the hydrogen flow. In several runs, 0.8 to 1.8 PCt of hydrogen sulfide was introuced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1949

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By E. S. Machlin

THE function of this paper is to present certain results based on the fact that the strain energy arising from the solution of out-of-size solute atoms into the solid matrix is free energy and not internal energy, and that this strain energy is almost wholly shear strain energy as Zener1 pointed out. One natural consequence of this fact is an expression for the excess entropy of mixing due to the strain energy. Also, a derivation of the integral molar free energy of mixing partitioned to strain energy will be made using the model of Lawson2 and thermodynamics. This derivation has the advantage of showing in a simple way the assumptions involved in Lawson's treatment. The excess entropy of mixing partitioned to strain energy can be derived in two ways. The first way makes use of the fact that the strain energy is almost wholly in the form of shear strain energy. In this case, as Zener1 pointed out, the change in entropy due to the addition of shear strain energy is to a first approximation given by ?S/?? p,T = - ?lnµ/?T p,? Hence, the excess entropy of mixing partitioned to strain energy will be given by Sx ? = ?S/?? p,T Gx ? = - ?lnµ/?T p,? Gx ? where, Gx ? is the relative integral molar free en- ergy partitioned to strain energy; S is the entropy; is the shear strain energy; µ is the shear modulus; T is the absolute temperature; p is the pressure; and ? is the shear strain. Zener,1 as well as others, has pointed out that the shear strain energy stored in a compressible isotropic solid due to the insertion of an off-size incompres-sible sphere into a spherical hole in the solid, is approximately given by 2/3 µ/O (O°I - O)2 where a is the volume of spherical hole and no , is the volume of sphere. If we now consider the introduction of one mol of such spheres into an infinite volume of solid, then the relative partial molar free energy excess due to strain energy alone is GM ? = 2/3 µ/v (v ° 1 - v)2 where v is the molar volume of solvent and v°1, is the molar volume of pure solute type 1. Let us consider that these spheres are the two types of atoms in a binary solution, then there will be a similar relation for solute 2. The total relative integral molar free energy excess due to strain is then, to the approximations stated above GM ? = GM ? x1 + GM2 ? x2 = 2/3 µ/v [(v ° 1 - v)2 x1 + (v ° 1 - v)2 x2]. Lawson's relation for the strain energy can be de-

Jan 1, 1955

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

By G. L. Oldright

THE metallurgist is familiar with the rapid development of concentration -by flotation and smelting in the reverberatory in recent years, brought 'about chiefly by the exhaustion of' bodies of .rich, coarse, direct smelting ore. Geologically speaking, in many porphyry-copper districts, the richer contact or replace let deposits surrounding 'the main ore-forming igneous intrusion have been exhausted, and it is necessary to beneficiate the copper minerals disseminated throughout the mass of the intrusion itself. The organization of great companies to treat such low- grade ores on a large scale and the practices resulting from the necessity for an economic method of treatment 'are among the most prominent metallurgical developments of the past decade. It is interesting to note the effect of the present trend of practice on the inter-relationship of the concentrator and smelter, on the constituents of the smelter charge, and on smelting in general.

Jan 1, 1925

By James Pollock

The possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. Possibility of Collodial Deposition While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. Evidence of Colloidal Deposition Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances—at Steamboat Springs, Nevada, and Sulphur Bank, California—hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1949

By James Pollock

The possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. Possibility of Collodial Deposition While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. Evidence of Colloidal Deposition Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances—at Steamboat Springs, Nevada, and Sulphur Bank, California—hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1949

By C. M. Moncrief, B C. Craft

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By C. M. Moncrief

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By James Pollock

SUMMARY THE possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. POSSIBILITY OF COLLODIAL DEPOSITION While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. EVIDENCE OF COLLOIDAL DEPOSITION Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances-at Steamboat Springs, Nevada, and Sulphur Bank, California-hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1944

BENEFICIATION AND CONCEN'TRATION; FROTH FLOTATION U.S. 4,069,144 - In the froth flotation beneficiation of phosphate rock using at least an acid flotation step and an amine flotation step, the crude ore is dried either during transport or storage or by air circulation immediately prior to classification, and the dried ore mixed with water and classified prior to flotation The preliminary drying substantially eliminates the usual problems with clay slimes G. C. Johnson and A. E. Schweizer, assigned to Mobil Oil Corp. Jan 17. 1978. 4 pp (209- 11) . Filed 1 1-19-75 (633,535).

Jan 1, 1979

By D. Weinstein

The high temperature mechanical properties of stainless steels after fast neutron irradiation are discussed in the light of effects caused by lattice dattmage and effects caused by helium generated from n,a transmutations. Embrittlement at high temperatures is due to helium accumulation at grain boundaries and to cavity formation and proPagation along grain boundaries. Following from the embrittlement mechanism, it is suggested that when deformation occurs by mechanisms associated with super plasticity, helium ac-curnulation at boundaries should be attenuated and cavities, if formed, should be nonpropagating. As the mean free Path between interphase boundaries of a two-phase Fe-Cr-Ni alloy was decreased, the degree of superplastic deforrnation at 870°C increased, as vneaszired by total elongation and by the expottent m = a log 'a/a log 'i. This alloy and type 304 stainless steel were cyclotron irradiated in an a-particle beam to a helium concentration of -1 x 10 atom He per atom. The stainless steel specimen was embrittled, but the ductility of irradiated two-phase Fe-Cr-Ni alloys correlated with the values of. m during 'defor-malion. The .finest grained, helium-injected specimens that deforrned with highest m values exhibited the largest elongations to ,fracture. These results could be correlated with metallographic observations of cavity behavior: the propensity for intergranular propagation was lessened as the m value increased. It is concluded that superplastic deformation is ef-fectizle in attenuating helium embrittlement at elevated temperatures. One of the principal problems associated with development of fast breeder reactors is application of alloys such that suitable fuel cladding results. Stainless steels and other Fe-Cr-Ni alloys, because of highly acceptable nuclear characteristics, represent the primary materials for this component, and an exhaustive research and development effort is being conducted. The main deficiency of these materials has been a severe loss of ductility at high temperatures after fast neutron irradiation. An extensive body of mechanical property data and microstructural observations has provided an adequate phenomenological description of embrittlement; in conjunction with transmission electron microscopy studies, a reasonably acceptable embrittlement mechanism has been obtained. Following from this mechanism, it is suggested in the present work that ductility would be enhanced if deformation could occur by mechanisms associated with the phenomenon of superplasticity. Experiments to test this hypothesis have been conducted, and the results are presented and discussed in this paper. IRRADIATION EMBRITTLEMENT AT HIGH TEMPERATURE Austenitic stainless steels have been irradiated to accumulated fast neutron fluences of 1020 to 1022 nvt at temperatures between 60" and 600°C. Specimens that have been exposed to these conditions and subsequently tensile tested at temperatures between 600" and about 900°C exhibit approximately 5 pct total elongation to fracture.'-3 For unirradiated specimens receiving a nearly identical thermal exposure, total elongation at these test temperatures is about 45 pct. Examination of irradiated specimens has shown that fracture propagation is entirely intergranular. These phenomenological aspects of irradiation embrittle-ment at elevated temperatures are well known and are not generally disputed. Although the explanation of this phenomenon has been controversial, a mechanism for ernbrittlement has emerged that accounts reasonably well for the observed mechanical behavior. The controversy resulted primarily from an indeterminate role of neutron-in-duced lattice damage, if any, and a presumed, but experimentally unverified, contribution to embrittle-ment from helium generated by n,a transmutations. Recently, Holmes and coworkers4 have conducted experiments that separate these effects, and the results are instructive in formulation of the ernbrittlement mechanism. Holmes el al.4 irradiated type 304 stainless steel in EBR-I1 to a fluence of 1.4 x 1022 nvt (E > 0.18 mev); the irradiation temperature was 538" * 48°C or, in terms of absolute melting point, 0.49 * 0.03 T,. After irradiation, tensile tests were conducted at temperatures of 21" to 870.C, the specimens first being annealed for 30 min at each test temperature. In addition, thin sections of irradiated specimens were annealed for 1 hr at identical temperatures, electro and examined by transmission electron microscopy. Thus, for a given temperature, it was possible to correlate mechanical properties with the defect structure. At room temperature, the yield stress of irradiated specimens was a factor of 2.5 higher than unirradi-ated specimens exposed to an equivalent thermal history. Electron microscopic examination of the irradiated specimen revealed a high density of lattice damage in the form of Frank sessile dislocation loops and polyhedral voids. Holmes et al.4 concluded that the presence of this defect substructure caused the increase in yield stress and that after irradiation in a fast neutron flux at 0.49 Tm, substantial lattice dam-age persists. Annealing at progressively higher tem-

Jan 1, 1970

By C. C. Harris

This article presents a general equation describing the xYt surface in batch grinding. This equation contains as special cases most of the relationships which have been deduced from kinetic studies. In an earlier paper an analytical solution of the integro-differential equation of batch grinding was proposed1 as a first approximation of the xYt surface.' A more general equation will be presented here, which appears to combine in a single statement many conclusions reached by experiment. A possible underlying mechanism is that the changing product fineness leads to changes in the particle crushing strength and in the probability of encounter with the crushing media.

Jan 1, 1969