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By R. F. Mitchell, G. F. Dillon, A. F. Armington

In this paper the present methods of boron preparation are discussed with emphasis on the iodide intermediate. Several methods of boron triiodide preparation were investigated, the most satisfactory method being the preparation from the elements. A yield of 60 pct based on iodine is found for this method. Zone-refining, sublinzation, distillation, and fractional-recrystallization results are given for the boron triiodide, with distillation producing the best results. Several methods of decomposition are also discussed. The purity of the resulting iodide boron approximates the puritjl of the best available bromide boron, ELEMENTAL boron has been suggested as a possible high-temperature semiconductor by several workers,' but has never been exploited as a device material. The principal difficulty with boron is the unavailability of pure crystalline material from which accurate information on electrical properties could be obtained. Most boron crystals presently produced are very imperfect in structure and of questionable purity, particularly in relation to carbon content. Several methods of boron purification have been reported in the past few years, all of which produce material with a purity better than 99.0 pct. Most of these methods have been the subject of a recent review by Starks' and will not be elaborated upon in this report. However, of all the purification methods reported, only those using halide intermediates produce a purity approaching that usually required for electronic applications. The bromide intermediate has been most used for the preparation of high-purity boron.'y3 This material is easily prepared from the elements and can be effectively purified by distillation and decomposed by hydrogen reduction. The resulting product contains a trace of silicon, and an uncertain amount of carbon, believed to be approximately 100 ppm. It has been recently reported by Russian workers that high-purity boron can be produced using an iodide intermediate.' In the work cited, boron is reported free of spectro-scopically determined impurities, but the reported detection limits are quite high (- 100 ppm). In addition, no data is given on the carbon content of the product. In the present paper, boron triiodide was chosen as the intermediate for several reasons. First, carbon tetraiodide, which could be a major impurity, is reported to be unstable above 200" and hence could be easily separated from the boron triiodide by its decomposition, since temperatures greater than this are attained during the purification process. The low melting point (45°C) and boiling point (20B°C) and the relatively high vapor pressure of boron triiodide should allow the application of any physical purification technique to the material. The possibility of a lower decomposition temperature than that used for the bromide process is another advantage which might cut down extraneous contamination. The iodide, however, does have certain disadvantages when compared with the bromide, the production cost being the most significant. This is the result of a higher halide-to-boron weight ratio, which means more intermediate must be employed. The cost of the starting material is also greater for the iodide. This cost could be considerably reduced however, by recycling the iodine byproduct. Epitaxial growth of boron, which is probably the best method of producing junctions, should be possible with either the bromide or the iodide as the intermediate. However, this has been attempted only on a limited scale up to the present time because of the unavailability of good crystals. The authors have been relatively successful in laying down a heterotaxy of boron on silicon, however. This will be reported at a later date. Several crystalline modifications have been reported for boron, four of which are now believed to be real.' These are the a! and 0 rhombohedral and the a, and 0 tetragonal. In general, the a! rhombohedral is the low-temperature form and the B rhombohedral is the high-temperature form. The tetragonal structures are detected between 1000"

Jan 1, 1964

The earliest record of production in this county is for drilling a salt well in 1809. Some scattered data are shown in the table; the total figures are estimated. Little coal could be shipped in this period on account of lack of transportation. [ ]

Jan 1, 1942

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By C. D. Broadbent

Open pit blasting can be a low cost routine or a high cost bottleneck depending on geology, environment and the operator's ability to master site conditions. Because blasting is a repetitive operation, there should be ample opportunity to optimize the process; but ordinarily this optimization is rarely achieved and then only if conditions remain consistent and predictable. Often, however, and particularly with porphyry coppers, hidden differences in rock characteristics nullify the operator's best efforts. At a porphyry copper deposit being mined by Kennecott Copper Corporation, all of the following rock types occur; oxidized and fresh porphyry, altered and silicified limestone, explosion breccia, rhyolite, sandstone, shale and several others. The units can cover large areas or be limited to a few tens of feet in maximum dimension. They are rarely visible on the bench surface and often do not show up in the bench slope. Even though the blastability of these rocks varies substantially, a generally-uniform blasting pattern was formerly used with disappointing results. Secondary blasting was often required and high bottoms occurred frequently, overblasting wasted drilling time, and explosives caused excessive throw.

Jan 4, 1974

By H. E. Lee, P. C. Feddersen

846 . . . Metals Transactions, Vol. 185 T. J. WOODSIDE*—In the paper it was stated that many of the A. S. and R. plants probably used a process patented by Roscoe Teats in 1930. I might describe

Jan 1, 1950

By M. E. Volin, F. H. Erbisch, G. M. Wenberg

Bacterial leaching of copper and uranium is practiced under acidic conditions in environments furnishing sulfur and iron. However, many mineral deposits do not have these conditions; the chalcocite and native copper deposits in Michigan's Upper Peninsula are examples. Species of bacteria and fungi isolated previously from samples taken at the White Pine Copper Co. tailings pond and mine, were screened for solubilization of copper from chalcocite ore and flotation concentrate and from native copper jig concentrate. Certain Penicillium species solubilized significant amounts of copper under neutral to slightly acidic conditions in a carbon and nitrogen-enriched medium. Leaching apparently was accomplished by release of metabolites which chelated with the copper. The copper yield was highly dependent upon the medium composition and the concentration of copper in the source material. The standardized procedures which were developed in an attempt to maximize copper yield in leaching times of three to five days are described. This preliminary research indicates a biological leaching process for copper which is different from those in use, but whether it can be applied economically remains to be determined.

Jan 1, 1972

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

A plan which has just been approved by President Wilson, by, the Secretary of the Navy, and the Naval Consulting Board, provides for the active cooperation of the Associated Advertising Clubs of the World with the 30,000 engineers who will soon undertake the task of making a card index survey of American industry, so that it may be prepared for national defense, if need comes. Herbert S. Houston, President of the Associated Clubs of the World comments on the plan. "Through the great power of advertising we expect-to arouse manufacturers, workingmen, businessmen, in fact the whole country, to the vital need of making industry the basic line of defense so that, if necessity arises, it can supply munitions quickly and abundantly. "This is not a war measure, but a peace measure. The militarist will support it and so will the pacifist, as well as the great body of Americans in between. So the slogan `national defense and international peace, has been adopted believing that the two causes will be best served by linking them together. "While the primary thing, of course, is service to the country, it is manifest that this work of the engineers will be of the greatest service to industry in times of peace. If industry is mobilized for defense, it will be placed on a basis of efficiency to meet the keen competition that will surely follow the present war." Howard E. Coffin, one of the leaders of the American automobile industry, in outlining the far-reaching plans of his committee, the Committee of Industrial Preparedness of the Naval Consulting Board, said: "At the outset I wish to emphasize the absolutely non-partisan nature of this work. I am not even familiar with the political affiliations of the great majority of the members of the Board or of my committee. In setting out to, mobilize the industrial resources of the United States, we are concerned only with the benefit to the nation, and to that end we have called into being an organization made up of the best technical and business brains of the country, and that organization will work along business lines with strictly business methods. I think it reasonable to say that this is a movement perhaps unique in the history of national governments, and one geared up to the highest standards of twentieth century efficiency. "It is vitally necessary that American industry be made aware of the part it must play in the national defense. Our whole conception of warfare has been changed almost overnight. Our military heads at Washington are largely, of course, graduates of the very best technical schools, have been taught the profession of fighting, and are masters of that profession. As members of the Naval Consulting Board, we are unable to tell these men how to do their work. But while these departmental heads have lived with military problems all their adult years, we on the other hand have slept and eaten and lived with the industrial problems of the country. The two questions are wholly distinct, and the masters of one cannot possibly be the masters of the other. We are confronted then with the necessity of interlocking these two vast elements of our national life into a great working organization for the national defense. It is that which we are about to do.

Jan 5, 1916

By Michael A. Gustafson, Fernando B. Sotelino

INTRODUCTION The degree of success of any new project will ultimately depend on two factors: (i) the underlying economic strength of the project; and (ii) how successfully the parties involved can coordinate their interests to establish a financing structure which indeed capitalizes on the project's inherent economic attractiveness. A project's underlying economic attractiveness is determined by its inherent comparative advantage in accessing the factors of production, combining these factors of production to create a product and marketing this product. Initially, the decision regarding whether to go ahead with the project - the go/no go decision - has to be based on its total ability to generate cash flow returns to project participants to compensate them for resources committed and risks undertaken. The extent to which project sponsors will actually benefit from the project's inherent economic attractiveness is fundamentally dependent on their ability to establish the long-term financing arrangement which best meets the objectives and constraints of each project participant and sources the most advantageous funding. The decision regarding the financing of the project, the "how-to-go" decision, is then an attempt to find the capital structure, consistent with market terms and conditions and sound financial management policies which will best: (i) match planned outflows with cash inflows; and (ii) maximize the return for project sponsors. This article makes use of a case study to illustrate the analytical process involved in dealing with the go/no go and the how-to-go decisions on a project. Though most commonly applied to project finance situations, the guideline described herein is equally applicable to other financing situations, such as leveraged buyouts and debt restructurings, where timely repayment of debt depends largely on the future cash flows to be generated by the entity being financed. Our case study is of a hypothetical expansion of an existing copper mining operation in Latin America. The company, Latin American Copper (LAC) currently has 147 million metric tons of proven sulphide ore reserves. The existing mine complex consists of an open pit mining operation and a conventional flotation plant with a processing capacity of 20,000 metric tons of ore per day. LAC sells copper concentrates primarily to Japanese custom smelters. The mine has been in operation for 5 years, fine copper production last year was 108,240 metric tons, and LAC currently has assets of $175 million and net worth of $135 million. Due to a recent increase in proven reserves, LAC is considering doubling the treatment capacity of its flotation plant to 40,000 tons per day, and expanding its mining capacity to meet the additional concentrator capacity (the "Project"). Project capital expenditures and incremental working capital have been estimated at approximately $210 million. The construction period is expected to cover one year, including a three-month start-up phase. The Project is to be funded by a combination of equity, senior debt, including both supplier credits and/or commercial bank term loans, and subordinated debt. LAC's shareholders are willing to commit a maximum of $50 million to the Project. A government development agency, which is also a minority shareholder, might be willing to lend approximately $40 million to LAC in the form of subordinated notes, depending on the ability of the Project to generate foreign exchange reserves. Commercial banks cannot be expected to offer loans with maturities longer than ten years. The Project is expected to increase the value of the firm because: (i) It will solidify the Company's position as a low-cost copper producer by taking advantage of economies of scale. As a result of the expansion, cash production costs are expected to decrease 7.0[c]/lb. and all-in costs 11.0[c]/lb; (ii) The potential earnings stream from the sulphide ore reserves will be realized

Jan 1, 1985

By Martin J. Conway

DURING the past year, the intense interest shown by the metallurgical industry in the use of relatively pure oxygen has been evidenced by the number of papers dealing with its application and production. The reason for this interest is apparent when it is realized that, weight for weight, oxygen enters into the formation of steel equally with iron. In the manufacture of steel, approximately one ton of oxygen is required to produce one ton of ingots. Until the recent development of plants capable of producing oxygen at far lower costs than had ever previously been considered possible, the oxygen required for steel manufacture was used as it occurs in air, where it is associated with approximately four times its volume of nitrogen. Because of the diluent nitrogen more than 4 tons of total gaseous material per ton of steel must be handled rather than only approximately one ton required when pure oxygen is used. In addition, provision must be made to handle the large quantity of waste, gases resulting from the process. There are cases where the reduction in gas volume alone can justify the installation of an oxygen plant.

Jan 1, 1947

By G. K. Engelhart

EFFECTIVE use of rotary kiln waste gases to preheat dry pulverized materials has been demonstrated in full-scale operation at the Allentown Portland Cement Co. plant, Evansville, Pa. Pulverized raw materials are preheated in suspension in the gas stream in a multi-stage counterflow process which draws the gases through a series of cyclone collectors. Upon entering the first cyclone stage the material, continuously delivered and suspended in the gas stream, is successively collected and resuspended until it discharges through the kiln feed pipe. Gas and material contact time is thus prolonged, providing a high degree of heat recuperation with a very low temperature differential between gas and material at the final stage. The suspension preheater, developed by Klockner-Humboldt-Deutz AG of Cologne, Germany, was first installed at the Norddeutsche Huette plant, Oslebshausen, Germany. Similar preheaters are now in operation at three other German cement plants. The first American installation, at the Allentown Portland Cement Co. plant, was designed and manufactured by Fuller Co. of Catasauqua, Pa., Humboldt's licensee for the United States, Canada, and Mexico.

Jan 4, 1954

E. S. BARDWELL,* Great Falls, Mont. (written discussion ?).-There are several points in. connection with the manufacture of ferromanganese in the electric furnace which it seems to me. might prove of interest in this connection. Recent observation of a, number of electric furnaces varying considerably in size and transformer capacity, and all working under the same conditions, shows the small furnaces to be much more efficient in operation than the large furnaces. The furnaces examined were all of the same type. The crucibles consisted of tanks varying in size from 71-z by 15 ft. by 4 ft. deep, to 12 by 20 ft. by 9 ft. deep, with linings formed of carbon electrode butts. The smaller furnaces had transformer capacity rated at 1500 k.v.a.; the largest furnace had a transformer rated at 3000 k.v.a. All of the furnaces were operated on three-phase, 60-cycle current, the three electrodes being in a straight line. The voltages varied from 65 volts in the smaller to 100 volts in the larger furnaces. The charges consisted of manganese ore, coal, iron turnings, and limestone in proper proportions. The small furnaces, operating at low voltage, were making good recoveries. The slag loss was low and the volatilization loss almost nil. The larger furnaces, operating at higher voltages, showed increased loss of manganese in the slag and greatly increased volatilization loss when working on the same charges as the smaller furnaces, or on charges similarly calculated. The exact reasons for this state of affairs are difficult to state; a number of factors probably contribute to the results obtained in the large furnaces. First as to the effect of the higher voltage on manganese content of the slags. Increasing the voltage of the furnaces apparently tends to promote irregular working. The current takes the path of least resistance; this means superheating in certain areas in the crucible and insufficiently high temperatures in adjoining areas. The partially reduced manganese in the cooler areas passes into the slag and escapes further reduction.

Jan 11, 1918

By R. Adair, W. R. Hudspeth, W. T. McDaniel

D. C. Ralston (U. S. Bureau of Mines, Washington, D. C.)—Flake mica can be beneficiated by a wider variety of methods than almost any known mineral. However, most of these methods are not recorded. It is therefore a pleasure to find a written record of another application of a new method of beneficiation. The fact that the Humphries spiral gives a concentrate containing the mica flake mixed with the slime and small grit has forced a further separation by screening, in which the finest of the flake will pass through. Fine flake has its uses and if mixed with slimes or clay is recoverable reliably only by flotation. This loss must be charged against the spiral. On the other hand, the new muscovite mica paper recently brought out by General Electric Co., can be made only with grit free flake larger than 50 mesh. It is of interest to learn from the authors whether the washing of the flake on a 50 mesh screen can take the grit content below 1 pct, to meet this new demand. Must another degritting process be used on the flake, like electrostatic treatment of the dried material? H. D. Snedden (The Humphreys Investment Co., Denver)—When recovering mica in the spiral, gangue particles coarser than 16 mesh can be rejected more readily when operating at a high pulp density (35 pct solids) or a low volume rate (—15 gpm). A launder screen as used by Lehigh Coal Co. has proved very satisfactory to partially dewater the mica concentrate and to reject any gangue slimes it may contain. Under certain conditions mica cleaning in the spiral can be improved by reagentizing the spiral feed, the object being to insure wetting of the gangue minerals and to agglomerate or prevent wetting of the mica particles. R. B. Adair (authors' reply)—The grit content of the mica recovered on Humphreys Spirals varies with the fineness of the launder screen used to clean the mica product. Normal practice has been the use of 80 mesh screen, which will produce a mica product of acceptable grit content for most purposes. By using a 50 mesh screen, and increasing the screen area per ton of feed, it is felt by the authors that a mica of 99 pct plus purity could be obtained. This statement would hold only in the case of mica feed which was well de-laminated, and free from "clay balls," (semikaclinized feldspar), which tends to follow the mica through the process.

Jan 1, 1952

By M. S. Azun

I do not at all agree with the basic points of the author's conclusion. The use of lognormal or normal model to respond to the attribute distribution function should be carefully questioned. If fitting a distribution function of regionalized variables is the main purpose, one may employ one of certain well-known families of distributions, such as Tukey's lambda functions. For instance, the distribution function of gold assay values studied by Krige (Krige, 1978) may fit the lognormal model well, but one should not exclude that the basic idea of using the distribution function of observed data is to have insight of the physical mechanism that gives rise to the regionalized variables. In Applied Geostatistics, there are many examples considering only lognormal or normal model for the distribution function of geostatistical data even if the observed distribution function has more than one mode. Of course, using lognormal or normal model always brings easy computation for the statistical properties of attribute under investigation. Still, I object to adopting any of those models without having any "statistical inference." As seen from the author's paper, lognormal and normal model produce the same average grade (0.746% copper) and almost the same sample variance. Therefore, which model explains the probabilistic behavior of ore deposit is always an important question that should be replied by the geostatistician using not the common sense but the statistical and probabilistic methods. For kriging procedures, such as linear kriging, one should describe either second order stationary properties or bivariate properties of regionalized variables. Second order properties, such as correlogram function or semivariogram function, are the inputs of the so-called kriging equations. Selecting one of any useable models for the observed second order properties, such as spherical model, is not easy since the models are not based on the correlations structure of the regionalized variables. How those models being used in Applied Geostatistics can be distinguished is another important problem. One may develop many fitting models to respond to the observed second order properties of regionalized variables. However, I suggest that the model should be based on the probabilistic behavior of geologic process. The author used spherical model for copper, wolfram, and silver grades from isotropic sector (Fig. 2, 4, 3b) and exponential model for silver grades obtained along raises in isotropic sector (Fig. 3a). It seems that those semivariograms given in Fig. 3b for isotropic sector and Fig. 4 may be described by the random model implying that regionalized variables do belong to renewal process (Azun, 1983). If I knew the total number of data points used in estimation, may prove that my conclusion is correct. Recalling the test for the first order sample correlogram value, the test procedure is introduced such that the independence is rejected if [Ir(1) I > Za/2 N1/2] where Za/2 is the a/2 percentile of standard normal random variable and N is the total number of samples used in estimation (Azun, 1983). For the other observed semivariogram functions I suggest the author might try to use the so-called "Markovian model" describing not only the correlation structure of regionalized variables, but also the physical mechanism that produces the regionalized variables. The Markovian model for correlogram function is, [p (h) = T 1ih , h>1 ,] The Markovian model for the other second order properties of ReV are also derived. [T veß], in the above equation, show, for example, structural change and mineralizational variation in a considered deposit, respectively (Azun, 1983). In selecting any model, it is not easy to search for the "best" response to the observed second order properties of ReV's. The Markovian model, based on a theoretical understanding of underlying mechanism, gives more information about the occurrence of regionalized variables and respond to all properties. Random model and the so-called hole effect structure can be easily defined as a special form of the Markovian model (Azun, 1983). An estimation of any second order properties of regionalized variables may be computed through (N-1) lag. However, the dependency between the regionalized variables may be deemed to have "died out" after the so-called stationarity width (range). In practice, the estimation is carried out through 25% of the total number samples available. Therefore, the large fluctuations around the zero level and variance for correlogram or covariogram function and semivariogram function, respectively, cannot be observed. Since the number of pairs involved in the estimation of higher second order properties is small, the estimation variance at those lags is large. There is no need to show higher order estimated second order properties. After using one of any kriging procedure for block estimation, the distribution function of average grades has the same mean as the drilling sample grades but

Jan 1, 1986

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By Gill Montgomery

The strong upward curve of fluorspar consumption continued through 1968, with domestic producers unable to furnish more than 30% of U.S. requirements. Stocks of all grades were quite short at all points during most of 1968. This resulted in price increases as both domestic and foreign producers sought to cover spiralling labor costs. Further increases are probable for 1969. All Illinois mines were closed by strikes in January and February. The strong trend in metallurgical imports reflects the increased use of fluorspar in steelmaking, as new oxygen process steel plants come into production. The growth of use of all fluorocarbon chemicals continues to require additional acid grade fluorspar, with military uses a major factor. Several new aluminum smelting facilities coming into production are adding to the aluminum fluoride needs, bringing further pressure upon the world supply of acid grade fluorspar. The world-wide consumption pressure on all grades of fluorspar is pushing prices up, and no end to the tight supply is in sight, even assuming that all the new projects cited here are finished on schedule.

Jan 3, 1969

By C. E. Birchenall, F. N. Rhines, L. A. Hughes

A. J. Shaler—I should like to congratulate the authors on the presentation of this paper, which we have been awaiting a long time. The view they have taken of the sintering process, namely that voids are comparable to particles of a second phase capable of dissolving to a slight extent in the metal phase, is an interesting but dangerous one. Pines has given a first-order solution of the problem and Has predicted a decrease in the concentration of pores near the surface. The authors of the present paper have experimentally demonstrated the second-order effects, that is, the diffusion of the space phase between voids of different sizes, and also the movement of atoms from highly curved parts of a void to less curved regions of the same void. I have recently calculated the rate of vapor-phase transport within odd-shaped pores in copper at 850 °C and found that probably at that temperature volume flow is the more rapid shape-changing mechanism. The authors of the present paper have found that at 1000°C, vapor-phase transport is dominant. There is no disagreement here, I think. The dominant phenomenon can easily be different' in different temperature ranges and with different pore shapes: I used a cylinder going to a sphere, not a tricuspid going to a "triple cuspidor." But there is some danger in the other art of the explanation, that is, in the study of the diffusion of vacancies from a pore to its neighbors and to the outside. A vacancy is very different in dimension from an atom. When it moves, it carries a field of elastic strain. This has to be taken into account. A concentration gradient of vacancies can cause them to diffuse. But in the absence of such a gradient, they can be made to diffuse by a field of stress. What happens in some of our experiments, and it is most noticeable in the shrinkage of synthetic cylindrical pores, like the tubes we have been working with, may be broken down into the following steps. (1) The presence of a surface establishes a vacancy concentration gradient, as Dr. Kuczynski and the present authors have shown. (2) Vacancies then diffuse in order to decrease this gradient. (3) In so doing, they cause an elastic field to be built up in such a direction as to oppose the diffusion, so that it slows down until it reaches a steady-state rate. (4) The steady-state flow is due to the fact that the surface tension acting on curved surfaces applies a stress to the system which itself mechanically causes vacancy diffusion. What I have said is that the diffusive types of flow of the authors and of Dr. Kuczynski are transient phenomena which soon stop if the pores are large. We are then left with a mechanical problem only, and our researches have not yet disclosed just what the mechanism of flow is; it may be a slip process, or it may take place by a vacancy diffusion of the type Nabarro has de-

Jan 1, 1951

By R. W. Fenn, H. A. Lepper, W. R. Hibbard

A. J. Shaler—I should like to congratulate the authors on the presentation of this paper, which we have been awaiting a long time. The view they have taken of the sintering process, namely that voids are comparable to particles of a second phase capable of dissolving to a slight extent in the metal phase, is an interesting but dangerous one. Pines has given a first-order solution of the problem and Has predicted a decrease in the concentration of pores near the surface. The authors of the present paper have experimentally demonstrated the second-order effects, that is, the diffusion of the space phase between voids of different sizes, and also the movement of atoms from highly curved parts of a void to less curved regions of the same void. I have recently calculated the rate of vapor-phase transport within odd-shaped pores in copper at 850 °C and found that probably at that temperature volume flow is the more rapid shape-changing mechanism. The authors of the present paper have found that at 1000°C, vapor-phase transport is dominant. There is no disagreement here, I think. The dominant phenomenon can easily be different in different temperature ranges and with different pore shapes: I used a cylinder going to a sphere, not a tricuspid going to a "triple cuspidor." But there is some danger in the other art of the explanation, that is, in the study of the diffusion of vacancies from a pore to its neighbors and to the outside. A vacancy is very different in dimension from an atom. When it moves, it carries a field of elastic strain. This has to be taken into account. A concentration gradient of vacancies can cause them to diffuse. But in the absence of such a gradient, they can be made to diffuse by a field of stress. What happens in some of our experiments, and it is most noticeable in the shrinkage of synthetic cylindrical pores, like the tubes we have been working with, may be broken down into the following steps. (1) The presence of a surface establishes a vacancy concentration gradient, as Dr. Kuczynski and the present authors have shown. (2) Vacancies then diffuse in order to decrease this gradient. (3) In so doing, they cause an elastic field to be built up in such a direction as to oppose the diffusion, so that it slows down until it reaches a steady-state rate. (4) The steady-state flow is due to the fact that the surface tension acting on curved surfaces applies a stress to the system which itself mechanically causes vacancy diffusion. What I have said is that the diffusive types of flow of the authors and of Dr. Kuczynski are transient phenomena which soon stop if the pores are large. We are then left with a mechanical problem only, and our researches have not yet disclosed just what the mechanism of flow is; it may be a slip process, or it may take place by a vacancy diffusion of the type Nabarro has de-

Jan 1, 1951

By Thomas R. Smith

This paper covers oil shale resources in those countries that border the Pacific Rim. The major known resources around the Pacific Rim occur in the Western United States, Australia, the People's Republic of China, (PRC) and the Thailand/Burma region. The location of these deposits is shown in Figure 1. In 1965, the U.S. Geological Survey estimated world oil shale deposits of over 4 quadrillion tons having a potential oil yield of over 2 quadrillion barrels. If all this were extracted, it could meet the world's entire energy needs far into the future. However, the Survey also estimated the spent shale waste could cover all of the surface of the world to a depth of about 10 feet. Thus, for this and many other technical and economic reasons, it does not appear to be feasible to develop a large portion of the world's oil shale resources in this century; nor will shale in itself solve our energy problems. Nevertheless, shale oil and other ' synthetic fuels are expected to play an important role in new energy supplies in the longer term. WHAT IS OIL SHALE OR SHALE OIL? The term "oil shale" is sometimes a misnomer, in that the rock is often more of a limestone or siltstone than a shale. The common link between resources termed “oil shale" is that they all contain an insoluble substance cal led kerogen (which is from the Greek words for waxmaking). Kerogen is a form of organic carbon derived from a variety of plants ranging from algae to higher plants. When heated sufficiently, the kerogen generates hydrocarbons called shale oil, a form of synthetic crude oil that in most cases is lower in hydrogen content than conventional crude oil. The amount of oil in oil shale is relatively small --roughly 10 percent (by weight) in the richer shales. To upgrade this synthetic oil to usable products, additional processing is necessary. This brief sketch gives an idea of what this different, but significant, form of hydrocarbon is like. ENVIRONMENTS OF DEPOSITION Most oil shale deposits fall into three environments of sediment deposition: 1ake (called lacustrine), sea (marine) and river (fluvial-deltaic). In each case, the deposition of oil shales took place in quiet water environments where plant life, particularly algal plants, could flourish and, after dying, be deposited in unoxygenated water where the kerogen precursors would be safe from destruction by oxidation. The oil shales that were deposited in large lake basins (lacustrine) have attracted the most attention for development over the years. They often have multiple seams, deposited in a cyclic nature with extensive areal distribution and rapid vertical changes in kerogen content. Grades are moderate to high, ranging from 80 to 200 liters per tonne. Rundle in Australia and the Piceance Creek Basin in Colorado are examples of this type. Both deposits represent large volumes of oil shale in small areas which could provide the large volume of feedstock needed for future commercial operations. The stratigraphic sections of these two deposits feature thick oil shale seams with average grades of 80 - 125 liters/tonne conducive to both open pit, and underground operations. However, the rock strength of the Rundle shale is not sufficient to - support underground mining. On the other hand, the Colorado deposits, being more carbonate in nature, are sufficiently strong to support either type of mining depending on the overburden to ore ratio. These latter types of deposits will likely provide the first target for development of a commercial industry. The marine type is characterized by extensive areal distribution with relatively thin seams. The grades are generally low to moderate, ranging from 50 to 120 liters per tonne. The marine oil shales are common worldwide, and their attractiveness for mining is dependent on the overburden to ore ratio. Because of their widespread areal distribution, their in situ resources can be quite large. The Toolebuc Formation in Central , Queensland, Australia is a good example of this type of deposit being 7-10 meters thick over an extensive area. The Julia Creek deposit with its favorable overburden-to-ore ratio is being studied for possible development. In a fluvial-deltaic environment, there are many small lakes or bogs associated with rivers in which a very pure type of oil shale called torbanite could form. Torbanites are very high grade containing up to 75 percent hydrocarbons. The known occurrences are generally small lenticular deposits associated with coal seams. Even with the high grades, it is not likely that any of the known deposits would warrant commercial development because of their small size. The torbanite deposits in New South Wales, Australia were processed prior to World War I1 near the town of Glen Davis. However, today's known resources of this type are not large enough to warrant a commercial plant.

Jan 1, 1982