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By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,'-* iron,' and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By Kenneth M. Bravinder, Jonathan E. Koogle, Dean H. Sheldon

THE solution of subsurface geological problems requires an analysis of vertical and horizontal dimensional relationships. For many, the ability to visualize structures in three dimensions is not easily acquired, and for areas where the structural conditions are complicated by faulting the need arises for illustrative models. This has led to the many forms of peg models, in which the usual course of construction includes a peg for the well bore, and the suspension of strings from peg to peg to illustrate the formation correlation between wells, thus developing the usual folds and flexures. Such models proved unsatisfactory for the analysis of fault problems. Consideration was then given to the use of transparent materials. A model of the Dominguez oil field was constructed in 1935, which consisted of a series of glass panels from well to well on which the formations were shown in color. This model, though serving its purpose at the time, proved to be impractical from the standpoints of cost, breakage hazard, and extreme difficulty in maintenance. The cost of materials was estimated to be approximately $300, and the construction required the services of one man for a period of from 10 to 12 months. Maintenance after actual construction was an additional expense. Consideration was then given to the use of celluloid, and after some experimental work it was found that the advantages in its use were: (I) a short construction time, (2) ease of handling the material, (3) sections are easily reworked, (4) low cost. CONSTRUCTION It would be of little value to recount here the difficulties encountered in the building of the first celluloid model. The conclusions drawn, however, suggest the following procedure for those who contemplate the construction of such a model: I. Determination of the Scale.-Accurate geological interpretation requires the use of the same scale horizontally and vertically. It should be emphasized that the limited size of the celluloid sheets (20 by 48 in. maximum dimensions), the area to be studied, the maximum depths to be plotted, and area of possible future development are the controlling factors in adopting a scale to be used. 2. Construction of the Base.-A satisfactory base may be constructed by using two pieces of three-ply wood separated by strips of i by 2-in. material. This type of construction prevents warping of the base. The size of the base is determined by the dimensions of the area to be studied plus 5 in. on all sides. A map of the same scale as that adopted for the model, indicating the lines of section to be used, should be fastened to the base. 3. Construction of the Frame (Fig. I).-In the construction of the frame the use of 1/2-in. o.d. pipe welded in a box shape is suggested, with two horizontal rods on each of the four sides, top and bottom. The top rod should be at least I in. higher than the

Jan 1, 1941

By B. D. Lichter

The lattice parameters of zirconium and zirconium-oxygen solid solutions (hcp) were determined from measurements of back-reflection X-ray photograms obtained at 29°C using a symmetrical focussing camera. The following linear equations between parameters (c,a) in angstrom units (10-8 cm) and atom ratio (m) of oxygen to zirconium were obtained: c = 5.14764 + 0.2077m a =3.23168 + 0.1099m. The linear equations given are valid over the range 0 to 5 at. Pct 0. The accuracy of individual parameter measurements approaches the limiting accuracy determined by the spectral broadening of the incident characteristic radiation, and exceeds the accuracy of previously reported values. THE present work was undertaken in order to determine the lattice parameters of zirconium-oxygen solid solutions with an accuracy that allows quantitative determination of oxygen in zirconium. The results indicate that this is possible if very careful measurements are made, since the parameter change is only a few hundredths of a percent per at. pct 0.1, 2 In the present investigation the desired accuracy was achieved with large-grained samples using a back-reflection focussing camera and maintaining good temperature control during exposure. In addition a digital computer was used for calculation of the parameters by means of an analytical extrapolation.37 Suitable diffraction photograms were obtained from large-grained samples by using a modification of the technique described by Graf and Monteil.5 This consists of simultaneous rotation and oscillation of the specimen about two mutually perpendicular axes during exposure. Whereas, normally the upper limit of grain size is about 50 µ for useable diffraction photograms, this technique allows extending the upper limit of grain-size to exposure of a single crystal. EXPERIMENTAL Preparation of Alloys for X-ray Diffraction—Zir-conium, designated as hafnium-free, Westinghouse "Grade 1," was swaged from l/2-in.-diam crystal bar to 3/8-in.-diam rods. Substantially all of the hydrogen was removed from the zirconium by annealing at 1200°C in a high dynamic vacuum. The rods were then swaged to 0.2 in. diam without intermediate annealing, and 2 in. lengths were cut for alloying with oxygen. Samples for chemical analysis were taken from portions of the rods between each 2 in. length. Chemical analysis of the dehydroge-nated zirconium is given in Table I. Commercial tank oxygen (99.5 pct 0) was condensed in a liquid nitrogen-cooled trap, and part of the condensate was slowly reevaporated into 5-liter storage flasks. Nitrogen remained as a reactive impurity, and the calculated maximum increase in nitrogen content after a 5 at. pct 0 addition to zirconium was 50 ppm by weight. However, chemical analyses of several of the prepared alloys indicated that the maximum increase in nitrogen content was 10 ppm. The storage flasks, a Sieverts-type gas burette and manometer, and associated traps, pumps, and pressure gauges were connected through a glass high-vacuum manifold to comprise the gas addition system. A fused silica tube, connected to the mani-

Jan 1, 1961

By M. S. Burton, H. H. Kranzlein, G. V. Smith

The influence of up to 2 at. pct of Ni and Pt on the yield strength of mono- and polycrystalline high-purity iron has been evaluated at temperatures from + 25° to -196°C. Current theories of solid -solution strengthening fail to explain the experimental observations. The temperature dependence of yield stress was found to be less in the alloys than that in high-purity iron. The room-temperature yield stress increased with alloy content, but at —78°C the yield strength first decreased with increasing a1loy content. AS a result of many studies, a number of theories have been proposed for solid-solution strengthening. The purpose of the present study was to evaluate these theories, as applied to the solid-solution strengthening observed in Fe-Ni and Fe-Pt alloys. Of various theories of solid-solution strengthening, those of Cottrell,1,2 Fisher,3 Suzuki,4 and Mott and Nabarro5 are most prominent, and have been discussed widely in the literature.'-' Of the recent concepts of solid-solution hardening the work of Fleischer9 is notable. Each of these models has been applied to particular alloy systems with some success, but in general none has proved generally applicable. In many of the previous studies to assess the effects of alloy additions in ferrous systems, lack of adequate control of the purity and grain size of the materials has obscured strengthening effects, so that few comprehensive data relating composition, temperature, and change of lattice parameter have been determined. In the present investigation an attempt was made to obtain data which would be meaningful in evaluating the theories of strengthening. Materials of high purity were used to minimize extraneous impurity effects, and both single crystals and polycrystalline materials were studied to evaluate the effect of grain boundaries. Nickel and platinum were chosen as alloy additions, because both belong to the same chemical group and have the same crystal structure and valence, with markedly different atomic diameters. It appeared that some conclusions regarding atomic size effect on strengthening might be made. MATERIALS AND PROCEDURES Fe-Ni and Fe-Pt alloys containing 0.5, 1.0, 1.5, and 2.0 at. pct alloy additions were prepared from high-purity materials. The iron was supplied by the American Iron and Steel Institute from a stock of 99.98 pct zone-refined iron prepared by Battelle Memorial Institute. The minimum purity of the nickel and platinum used for alloying was 99.98 and 99.999 pct, respectively. Alloys were prepared by levitation melting, cast into cylindrical copper molds, and cooled, all under a partial pressure (0.3 atm) of purified helium. Samples were 0.375 in. in diameter and weighed 20 to 25 g. Chemical analyses of the alloys are given in Table I. A sample of unalloyed iron also was cast as a control specimen.

Jan 1, 1965

By C. E. McCarthy, A. George Stern, Stanley J. Green

The national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of 1914-18 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. Wyomingite Deposit For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the south- western part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, 12; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the Wyomingite has a potash Content averaging slightly higher than eleven per cent K2O. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1948

By A. George Stern, Stanley J. Green, C. E. McCarthy

The national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of 1914-18 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. Wyomingite Deposit For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the south- western part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, 12; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the Wyomingite has a potash Content averaging slightly higher than eleven per cent K2O. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1948

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18. 19. 21, 22, 23, 24, 30, 34). concluded that a foundation lor the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.I One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur 0. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 232,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. Stadler's Hypothesis Worthless It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left—the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things. that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in finc crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1943

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18. 19. 21, 22, 23, 24, 30, 34). concluded that a foundation lor the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.I One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur 0. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 232,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. Stadler's Hypothesis Worthless It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left—the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things. that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in finc crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1943

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By T. W. Smoot

Bentonites are composed chiefly of montmorillonites which are clay minerals generally distinguished from other clay minerals by their surface activity and extremely fine particle sizes. The uses of bentonite are many and varied, depending principally on one or more of the following characteristics: 1) Thixotropy, 2) Dispersion, 3) Plasticity, 4) Swelling, 5) Surface area, activity, ab- and adsorbtive properties. Some of the major uses of bentonite are briefly reviewed as are the mineralogical and physical properties. The uses of X-ray diffraction, differential thermal analysis and other tests for physical properties are reviewed as to their uses in evaluation. In the past 40 years, the industrial uses of bentonite have grown to include many applications. The physical and chemical properties of bentonites are such that they can be used as catalysts, adsorbants, plasticizers, binders, drilling muds, and pelletizers. Not all bentonites, however, can be used for all of these purposes and some are probably of little or no value for any use. The purpose of this paper is to briefly review the mineralogical, physical, and chemical characteristics and variations of bentonites. The determination of these characteristics and their uses in industry are also reviewed so that these determinations can be used as guides for evaluation. DEFINITION OF BENTONITE The word bentonite, as used in this paper, refers to a clay material, usually (but not necessarily) the result of the in-place-weathering of volcanic ash. Its mineralogical composition is dominated by the clay mineral montmorillonite and generally carries other clay minerals and silica minerals as the major 'impurities'. For this discussion, such a definition is justified since most of the economic uses of bentonite~ depend upon the physical and chemical characteristics of the montmorillonite minerals involved. The terms montmorillonite and bentonite have been used almost interchangeably in industry although the latter is much more commonly used. Therefore, where montmorillonite is discussed, it should be understood that the major feature of a bentonite is the subject. STRUCTIJRE OF MONTMORILLONlTE The economic importance of bentonites is generally based on one or more of the following characteristics of montmorillonite: 1) high-thixotropy and easy dispersion in water, 2) high-plasticity, 3) swelling properties, 4) large surface area/unit mass, 5) high surface activity, and 6) adsorptive properties. To understand these properties, an appreciation of the structural scheme of montmorillonite is helpful. Montmorillonite IS one of the three-layer clay minerals composed essentially of hydrous aluminum silicates. The essential building blocks of these layered silicate:; are: 1) silica tetrahedron composed of a silicon atom surrounded by four oxygen atoms, and 2) aluminun (iron, magnesium, etc.) octahedral unit that, ideally, has one of these atoms surrounded by six hydroxal units. Fig. 1 is a diagrammatic sketch of the montmorillonite structure. In the montmorillonite structure, the tetrahedron are pointed inward and attached to the octahedral units so that the O= atoms replace the hydroxal units where they are bonded; hence two-thirds of the hydroxal units

Jan 1, 1962

By H. L. Talbot, A. J. Hall, R. S. Young

A method for the chemical differentiation of oxidized cobalt from sulphide cobalt in complex mine and concentrator products is of considerable interest to a number of mining companies throughout the world. At Rhokana Corporation, in Northern Rhodesia, for instance, cobalt is found chiefly in the sulphide form, as carrollite, but a cobalt oxide mineral also occurs irregularly underground, and relatively small quantities in the mill feed from time to time are difficult to detect visually at the concentrator. The oxide cobalt is not amenable to the sulphide flotation process used at Rhokana and nearly all of it passes into the tailing. The occasional period when high tailing losses occur with no appreciable change in the cobalt content of the mill feed has naturally been disturbing to the concentrator staff, who had no means of determining whether an influx of cobalt oxide ore or laxity on the part of the mill flotation operators as responsible for these results. A procedure for determining oxidized copper minerals, based on their solubility in dilute sulphuric acid saturated with SO2, has been used for many years in the copper industry. In the presence of cuprite the procedure fails, but otherwise it gives results quite satisfactory for control pur- poses. Empirical methods for determining oxidized forms of zinc and lead have been proposed, but they are generally unsatisfactory except in isolated cases of a very simple ore. No published procedure for determining oxidized forms of cobalt or siinilar elements has come to the authors'notice. Experimental Procedure There are obviously two alternatives in attacking a problem of this nature. One is to employ a solvent for oxide cobalt that will not dissolve cobalt sulphide. The other is to find a substance capable of oxidizing the cobalt sulphide to sulphate, which of course is water-soluble and can then be leached from the water-insoluble oxide cobalt. A representative sample of Rhokana cobalt oxide ore was secured, ground to minus 200-mesh, and carefully rolled to furnish a standard sample for this work. The analysis of this material gave the following percentages: Co, 0.55; Cu, 1.64; Fe, 2.98; S, 0.08; SiO2, 41.42; Al2o3, 11.20; CaO, 13.82; MgO, 3.80. As a source of cobalt sulphide a similar large sample of carrollite was prepared, analyzing Co, 23.36 per cent; Cu, 27.32; and S, 31.13. This sample of course was not pure carrollite, but was the best obtainable in quantities sufficient for a standard intended for considerable work. It was a pure sulphide sample, microscopic examination showing only carrollite, a little bornite, and gangue, with no visible sign of oxidized ore present. A wide variety of reagents as used in an effort to selectively dissolve oxide cobalt or to oxidize sulphide cobalt to

Jan 1, 1949

By D. W. Fuerstenau, L. M. Berlioz

In 1957, Charles1 first presented an analysis of a relationship between the energy expended in comminution and the extent of size reduction achieved. Subsequently, Schuhmann extended and interpreted Charles' approach to comminution. According to their analysis, the energy, E, expended in comminuting unit mass of fairly uniformly-sized material is related to the size modulus of the product, k, by where a is the distribution modulus (slope of the log-log cumulative size distribution plot) and C is a constant, which is primarily determined by properties of the solid. If there is any fundamental basis for the E vs k relationship, E must necessarily be concerned with the useful work for the size reduction process and not necessarily the work input, as discussed in detail by Harris.3 Charles and numerous other investigators tested this equation only by relating k to the grinding time, assuming expended energy to be directly proportional to time, but never directly measuring power. In our laboratories, we recently constructed a special batch ball mill with which the power could be accurately determined with torque measuring apparatus.4 With this device, a direct test of the Charles relationship could then be made for ball milling. 5 EXPERIMENTAL A stainless steel mill, 11.5 in. long and 10 in. in inside diam, lined with eight low-silhouette lifter bars, was used for these experiments. The grinding media consisted of 30 kg of single sized, 1-in. diam, stainless steel balls, which occupied about 50% of the total mill volume under static conditions. The void fraction of the static ball load was approximately 0.4, and for the dry grinding conditions used, the corresponding interstitial volume was filled when about 3300 g of the dolomite feed material was present. The 7x9 mesh dolomite used as feed was obtained as a natural, uncrushed product thus as- suring a random distribution of feed particle shapes. Charge weights of 660, 1320, 1980, 2480, 3300, 3960 and 5280 g, which correspond to 20%, 40%, 60%, 80%, l00%, 120%, and 160% of the interstitial load, respectively, were used. Grinding times of 20, 40, 60, 80, 100, 150, 200 and 300 revolutions were considered, with the mill operating at 54 rpm (approximately 60% of critical speed). The tests were made sequentially, in that the size distribution obtained after a certain grinding interval was utilized as the feed for the subsequent period of grinding. Agreement with control experiments where the mill ran continuously for the entire interval was excellent. Torque measurements were made utilizing a Baldwin-Lima-Hamilton SR-4 torque pickup in the manner that has been described previously.3 Standard wet (to obtain the -400 mesh material) and dry sieving procedures were followed using the Tyler full screen series. RESULTS The Gaudin-Schuhmann size distributions obtained in all of these experiments are characterized by distribution moduli (slopes), a, of about 0.66 and are representative of normal dry batch ball milling of a material like dolomite. As an illustration of typical

Jan 1, 1968

By R. A. Cunningham, A. S. Murray

If a dense fluid such as mud or water is used for circulation, the formation drilled is influenced by a hydrostatic pressure. This pressure depends on hole depth arid drilling fluid density. Laboratory tests indicute that drilling rates in many forri~ations are decreased with increased pressure,—in some cases as much as 90 per cent. A comparison between laboratory and field tests indicates that drilling fluid head affects drilling rates in the field approximately the, same as in the laboratory. Drillirrg rates of many formations are increased by reducing drilling fluid head. INTRODUCTION For many years it has been noted that field and laboratory drilling rate tests did not agree even when the formations tested were the same. For instance, tests of some shales by the Hughes Tool Co. laboratory indicated drilling rates approximately 20 to 30 ft/hour, whereas in the ground this shale would drill only 3 to 5 ft/hour. A possible reason for this discrepancy is the effect of the high pressure which the drilling fluid exerts against the formation at the bottom of the hole. Consider a small element of rock (Fig. II that is to be removed by a rock bit. If the hole is filled with mud or water. the upper surface of the rock element is subjected to a pressure which depends on hole depth and fluid density. The mass of earth around this rock element presses against the circumferential surface and the lower surface. Because of the probability of shearing stresses between the rock element and the surrounding rock, this element is not under true hydrostatic stress. However, as a first approximation for test purposes the rock element was assumed to he under hydrostatic stress. The effect of hydrostatic pressure on some physical properties of rock has been studied.1,2,3 These tests show that the "differential" compres-sive stress:': necessary to cause rup- ture in rock cylinders is greater when tested under high hydrostatic pressure than when tested under atmospheric conditions. These tests were made with pressures greater than 20,000 psi which is in excess of those normally encountered in oil well drilling. Similar tests were made by the Bureau of Reclamation' using pressures equivalent to those encountered in oil well drilling. Again the "differential" compressive stress necessary to produce failure increased with increasing hydrostatic pressure. These tests indicated that drilling rates would probably decrease. Correlation between these tests and drilling tests was not practical. The purpose of this work is to study the effect of mud column pressure on drilling rate, assuming that the material drilled is in a state of hydrostatic strcss. This problem was initially investigated in the laboratory using variable bit loads and confining pressure;. Confirmation of laboratory results was obtained in the field from a series of carefully controlled drilling tests. Because of the necessity of testing many different types of formations. only results from representative formations will be presented here.

Jan 1, 1956

By Morris Muskat, J. M. McDowell

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By J. M. McDowell, Morris Muskat

In both production and refining operations of the oil industry many processes are controlled by the gas-liquid phase relationships of the hydrocarbon mixtures of interest. The quantitative behavior of fractionating or distillation columns and stills depends on the changes in the equilibrium distributions of the hydrocarbon components between the gas and liquid phases as the pressure or temperature conditions may vary along the length of the column or as the gross operating parameters and compositions are varied. In oil producing operations the nature and amount of gas phase developed within an underground reservoir as it is being depleted and its pressure declines also involve the basic equilibrium gas-liquid phase interactions. The influence of surface conditions of temperature and pressure and various separation procedures on the nature and amount of stock tank oil and natural gas recovered from a given well stream is likewise determined by the same basic phase equilibrium characteristics of the hydrocarbon systems. Such equilibrium separation of the gas and liquid phases in a well stream is of importance both in establishing optimum separator conditions for obtaining maximum stock tank oil yields and in the general problem of crude stabilization. The phenomena involved in these problems and their quantitative aspects can, of course, be established in each individual instance by appropriate laboratory experimentation. It has been found, however, that by associating with the individual hydrocarbon components functional characteristics de- scribing their individual gas - liquid phase equilibrium behavior, the phase properties of the composite mixtures can be predicted by mathematical computation. These characteristics have been termed "equilibrium constants", or "equilibrium ratios"," and are defined by the general equation: where K, is the equilibrium ratio for the jth component, y, is the rnol fraction of that component in the gas phase, and xj is the corresponding mol fraction in the coexisting liquid phase. Considering the Kj as representing available and measurable properties of the individual components of a mixture, and as defined by Eq. (l), it is readily shown that in a coexisting gas-liquid system the rnol fraction concentrations of the individual components in the gas phase, y,, and those in the liquid phase, x,, are given by the expressions: where the nj are the corresponding rnol fraction concentrations in the composite system, and ng is the mol fraction of the whole which is in the gas phase. The basic unknown in Eq. (2) is n,: which gives the gross separation between the gas and liquid phases. This may be determined in principle by imposing the requirement that the sums of the mol fractions in both the gas and liquid phases are unity, i.e. by the equations: The solution of the equivalent Eqs. (3) lying between 0 and 1, when inserted into Eqs. (2), provides a complete description of the compositions of the coexisting gas and liquid phases. While the Eqs. (3) are essentially equivalent to polynomial equations, such transformations are of little value when dealing with multicomponent sys-

Jan 1, 1949

By Karl J. Benecke

Though the first patent on a bucket wheel excavator (BWE) was granted in 1881 in the US, this technology was developed in Germany to the high standards of today. However, this development was only possible in parallel with development of shiftable belt conveyors and boom stackers. The combination of these three types of equipment in the open pits of the Federal Republic of Germany has made lignite the cheapest energy source for power generation, despite the low heating value of German lignite on the order of 8500 kJ/kg (3600 Btu/lb) only. Comparing the costs for fuels used in power generating on the basis of their heating value, the relation between lignite, high quality black coal, and imported crude oil is on the order of 1 to 1.5 to 2.5, hence highly in favour of lignite. These cost advantages for lignite in Germany are due mainly to the concentration of lignite mining in a few high-output mines. The largest one, Fortuna mine in the Cologne district, produced a total of 45 million tons of lignite in 1976. That equals the annual fuel need of a 5750 MW power plant running 7000 hours per year at full capacity. Altogether 95.2 million bank m3 equal to 200 million tons of overburden had to be removed to accomplish this lignite output. The largest BWE ever built is working in the Fortuna mine [(Fig. 1)]. At a digging height of 51 m above crawler level, the total vertical reach in relation to the face conveyor level is 98 m by means of its conveying bridge and loading unit. The hourly output is 10 400 bank m3. Its weight in operation is 13 000 tons and its wheel diameter 21.6 m, as high as a seven-story building. Major reasons for the development of BWE technology in Germany were: ? Lignite deposits with moderately consolidated, alluvial-type overburden (gravel, sand, loam, marl, clay, etc.) ? Great overall depth of the deposits, ranging far beyond 100 m, requiring a wide opening of the mine, hence not permitting direct overcasting of overburden. ? Multiple-seam deposits of poor-quality coal divided by reject partings, which demand a perfectly selective digging tool for clean separation. In general, these conditions are almost identical to those prevailing in the lignite deposits of Texas and neighbouring states: The type of overburden suitable for BWE digging, the overall deposit depth ranges down to around 100 m, and finally, the multi-seam occurrence with partings between seams, the latter ranging from just 1 m to a few meters in thickness. Technique As the Texas-type lignite deposits come into focus more and more as a possible fuel source in power plants to replace natural gas and crude oil, the following will deal with the BWE technology for mining a typical Texas lignite deposit under the aspect of producing enough fuel for a 500-MW power plant located at the mine mouth.

Jan 1, 1980

By C. E. McCarthy, A. George Stern, Stanley J. Green

THE national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of I9I4-I8 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. WYOMINGITE DEPOSIT For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the southwestern part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, I2; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the wyomingite has a potash content averaging slightly higher than eleven per cent K20. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1944