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By R. A. Generes, H. C. H. Darley

Laboratory tests showed that at elevated temperatures a reaction takes place between all metal hydroxides and clay muds, which results in a thickening or solidifying of the mud, the extent of which depends on the nature of the ingredients. Calcium hydroxide gave the strongest solidification whereas barium hydroxide only caused a mild thickening, indicating that the use of barium hydroxide muds instead of lime muds would be a good way of preventing high-temperature solidification. It was found possible to prepare barium mud in the laboratory with caustic soda and a thinner in the same manner as lime muds, and these barium muds had the same or better toleration of high solids content, resistance to salt contamination, and low gel strengths as the corresponding lime muds. Three field trials have been made with barium mud. The principal difficulty encountered was in determining the correct proportions of the tourly treatments required to maintain low gel strengths. A satisfactory systern was finally developed, and low gels were maintained throughout the third test. The wells on which the trials were made were not carried deep enough to test the resistance to solidification adequately, but oven tests at 350°F were made periodically and no tendency to solidification was noted except immediately after severe cernent contamination had introduced excessive amounts of calcium into the system. Although barium hydroxide costs considerably more than lime, the total mud costs were as low, and on the last well significantly lower, than the average cost of lime mud wells drilled in the vicinity. INTRODUCTION The advantages of repressing dispersion and hydra-tion of clay cuttings carried in the mud, particularly when drilling through thick clay formations, are well recognized. This repression is generally achieved by the use of lime, and lime muds have in consequence the desirable characteristics of high toleration of solids, low thixotropy, and good resistance to contamination. They have, however, the disadvantage of high-temperature solidification. This phenomenon has been described in detail by Gray et al, who have shown that it is the result of a chemical reaction between the hydroxides and the clay minerals. The work described in this paper was undertaken to find a substitute for lime which would not cause this solidification. LABORATORY EXPERlMENTS The principal positive requirement for a substitute for lime is that it should repress the hydration and dispersion of clay. It is well known that monovalent cations promote hydration while polyvalent cations repress it. Therefore, a few representative polyvalent salts and hydroxides were tested to determine whether they could be used as substitutes for lime. Their efficiency at repressing hydration and dispersion was measured by means of the clay-volume test. It has been shown elsewhere' that this test is a good measure of degree of dispersion of clay in suspension and that hydration accompanies and correlates with dispersion, so that measuring one measures the other. The test is made by centrifuging a 1:100 mixture of mud and 1-N NaCl and observing the volume of sediment—the greater the volume, the greater the dispersion. The tendency to caux solidification was measured by heating the muds in pressure vessels for 16 hours at 150°F and 370°F. An approximate quantitative

Jan 1, 1957

Jan 1, 1957

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months' furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957

By Edmonds W, Jeffcoat R

The completion of the first two open hearth furnaces in the new No. 2 open hearth plant at Port Kembla will increase Australian production of steel by 350,000 tons of ingots per annum.The paper gives an outline of the essential features of open hearth design and auxiliary equipment required to operate the two modern open hearth furnaces at present being installed.INTRODUCTIONThe increasing demand for steel required by Australian secondary industries led to the decision to construct and operate No. 2 open hearth plant at Port Kembla. Two basic open hearth furnaces of the most modern design are under construction and it is anticipated that these units will be commissi.oned in September 1956. Australian steel capacity will thereby be increased by approximately 350,000 tons of ingots per annum.PLANT LAY-OUT AND CONSTRUCTIONIn the design and lay-out of this plant the emphasis has been on efficient material handling with simplicity of design and operation. Overseas methods were studied and these studies, together with experience gained at Newcastle and Port Kembla open hearth shops, enabled this plant to be built to a standard which compares favourably with any other in the industry.Initially two furnaces, each of 2,75 tons capacity, have been built, but provision has been made in. the design and lay-out to enable expansion to six furnaces.The location of the new plant in relation to the existing units will be noted in Fig. 5. It is one of the first units to be built in an area which will dovetail into a pattern for...

Jan 1, 1957

By Robert G. Nisle

In conducting a pressure build-up test on an oil well, it is often necessary to shut-in the well for a short time prior to initiation of the test. The effect of such a short tern shut-in on the resulting pressure build-up curve is derived. The derivation is based on the Kelvin point-source solution and is a straight forward extension of the fundarnental theory. The magnitude of the effect is evaluatecl and illustrated by an example. It is shown that if the production subsequent to the short term shut-in is at least 10 times the duration of the shrct-in, the effect will he less than 10 per cent. INTRODUCTION It often happens that before a pressure build-up test can be made an additional valve must be mounted on the wellhead, or on arrival at the well, it might be learned that the well had been shut-in several hours the previous day because of a shortage of tankage. In such cases the question is How will such an interruption of production affect the results of a pressure buildup test This work explains how to take account of such a short term shut-in in order that the test can proceed without further delay. The solution presented here makes use of the Kelvin point-source solution used by Horne1 in his treatment of the pressure build-up in wells. Use is also made of the super-position theorem. MATHEMATICAL DERIVATION The well is assumed to have been in production at a constant rate for a relatively long time (several days or more). It is then shut-in for a short time, after which it is again placed in production at the previous constant rate. It continues to produce at this rate until shut-in for a pressure build-up test. The Kelvin point-source solution is expressed by Eq. 1. The sequence of production rates is listed in Table I. TABLE 1 — SEQUENCE OF PRODUCTION RATES Time interval Production Rate At time AT the pressure will be the resultant of the sequence of production rates shown in Table 1. An expression for the super-posed effects may be derived from this table. (Effect of + q for T + ? T) + (Effect of - q for T + ?T-t,) + (Effect of + q for T + ? T - t,) + (Effect of - q for ? T) = Resultant........(2) The desired result is obtained by substituting the effect defined by Eq. 1 for the terms in Eq. 2. The result is Eq. 3. When the logarithmic approximation is made for the exponential integrals and the terms collected the result is Eq. 4. Let T — t2 = T = flowing time following short term shut-in t2 — t1 = 6 = duration of short term shut-in Then T - t1 = r + 6 Substitution of these quantities in Eq. 4 gives p(rw ?T) = P,, -When d<<t - AT then d—&apos;-, T— approaches 1. r + AT In this case the effect of the short term shut-in may be ignored. In order to get some idea of the numerical magnitudes involved take the worst possible case, when AT = 0, that is at shut-in. If the error is made less than some maximum acceptable value at this time, it will be less than the maximum for all subsequent times. d + r Let the difference between the value of y-— and 1 be less than 0.1. Then —6+r — 1 < 0.1 S < O.l T Therefore, if the flowing time following a short term shut-in is at least 10 times the duration of the short term shut-in, the error introduced by ignoring the short term shut-in will not exceed 10 per cent of T+AT A T

Jan 1, 1957

By L. A. Willey

IN 1953, a method for filtering a liquid phase from solid phases while in equilibrium at elevated temperatures was devised at the Alcoa Aluminum Research Laboratories. Since then, it has been applied to the investigation of liquid-solid equilibrium in metallic systems. In application, the method simplifies the centrifuge filt.ration procedure as developed by Scheil and described by Gebhardt Fig. 1 shows a sketch of the filtering apparatus located within a thermal analysis furnace. It consists of a stainless steel filter crucible A, into the bottom of which a porous carbon filter disk B, 1 3/4 in. diam by 1/4 in. thick, is sealed to the shoulder and rim with carbonaceous cement. The base of the filter crucible, machined to an angle, fits into a tapered seat at the mouth of a stainless steel vacuum chamber C. A connecting tube from the vacuum chamber to a vacuum line also serves as a means for supporting the apparatus from the base of the furnace. An alundum crucible D of 25 ml capacity is placed with- in the vacuum chamber below the filter for collecting the filtrate. Two thermocouples E, in stainless steel protection tubes, which extend from 1/16 to in. above the center of the filter, are mounted on the rim of the filter crucible. One thermocouple is used in differential connection with the furnace control thermocouple to regulate rates of heating and cooling. The other serves as a means for recording the temperature of the alloy prior to filtering. A suitable mold coating is used on exposed surfaces of stainless steel parts to guard against attack upon these parts as well as to avoid contamination of the alloy samples. A mold wash prepared from precipitated CaCO, is suitable for aluminum alloys. The porous carbon for the filter disks and the carbonaceous cement, grade 200 (graphite base), were obtained from the National Carbon Co. Porous car-bon, grade Nos. 10 to 60, has been employed. Grade No. 40, however, appeared to give the optimum advantages in operation. In operation, an alloy sample is remelted and heated to about 50°C above its liquidus temperature. At the same time, the filter apparatus is preheated to about the same temperature. The alloy then is cast into the filter crucible.

Jan 1, 1957

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.&apos; Certain oxide minerals are also amenable to treatment by this type of oxidation.&apos; Several kinetic studies have been made of reactions of this type. Stenhouse&apos; found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen&apos; studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By R. V. Lundquist

Aeration in water slurries and controlled drying of manganous hydroxide produced from dithionate leaching of Artillery Peak manganese ores from Arizona were investigated by the Bureau of Mines at its Electrometallurgical Experiment Station, Boulder City, Nev., to determine whether a simple process could be developed for converting this product into a battery-grade manganese dioxide. The properties of manganese dioxide prepared by the thermal decomposition of manganous nitrate were investigated also. Manganese dioxide suitable for use in batteries was not obtained from the dithionate leach product, but some of the factors controlling its oxidation were isolated. Aging of manganous hydroxide was of major importance in retarding its oxidation by aeration. Sodium hydroxide and sodium silicate promoted oxidation by drying. Optimum quantities were about 0.85 mol of sodium hydroxide and 0.2 mol of sodium silicate per mol of manganese, and drying temperatures of 200° C. produced yields of manganese dioxide up to 90 percent of the manganese present. Higher temperatures and concentrations of reagents carried oxidation of manganese beyond its tetravalent state.

Jan 1, 1957

By I. Fatt

This paper proposes the network of tubes as a model more closely representing real porous media than does the bundle of tubes. Capillary pressure curves are derived from network models and pore size distributions are calculated from these curves. In this way is shown the difference between the true and calculated pore size distributions when the capillary pressure curve is used to obtain pore size distribution for porous media. INTRODUCTION Despite the technological importance of the laws governing flow through porous media, many of these laws have not yet been clearly formulated. This is especially true of the laws governing multiphase flow. The static properties, such as the capillary pressure curve, are also not at present interpretable correctly in terms of the pore size distribution and other structural properties of porous media. In the absence of any well founded theoretical description of fluid flow through porous media, many empirical descriptions have been proposed. In addition to the strictly empirical flow equa- tions, some equations have been developed rigorously from simple geometrical models of the pore spaces. These equations are only as valid as is the model used in their development. The two models used in the past, the sphere pack and the bundle of tubes, have been too simple, and as a result, the equations derived from them have failed to predict the observed properties. Agreement between theory and observation has been achieved for these models by inserting parameters of doubtful physical significance. The work to be reported here was undertaken in the belief that the study of a model more closely resembling most real porous media than does the sphere pack or bundle of tubes would yield useful information concerning the structure of real porous media and the relation between structure and flow properties. There was no intention of developing any calculational procedures, as for example calculating relative permeability from capillary pressure data. The objective of the study was instead to develop a better qualitative understanding of the relation between the various measurable properties of porous media. The model chosen for study is the network of tubes in which each tube represents a pore space in the porous medium. Microscopic observations leave no doubt that sandstones and clastic carbonates are three-dimensional irregular networks of irregularly shaped pores. The irregularity of these structures makes any accurate theoretical study of their properties impossible. Results from an oversimplified model such as the bundle of tubes are worthless when applied to real systerns. The sphere pack model, on the other hand, not

Jan 1, 1957

By L. Bombardieri, H. F. Mills

IRON KING mine, producing gold-silver-lead-zinc ore, is 10 miles east of Prescott, Ariz. At present the 1806 level is being developed. The echelon pattern of ore deposit continues at depth but is less pronounced, and the orebody is now more or less continuous over 2600 ft of strike length. with widths 5 ft to as high as 26 ft where overlapping of lenses occurs in one section of the mine. Better continuity of ore at depth has encouraged systematic mining and improved plant facilities to offset higher operating costs. With favorable persistence of ore at depth. the three-compartment No. 6 hoisting shaft appeared inadequate to handle increased tonnage from greater depths, and in 1952, a four-compartment steel and concrete shaft was started. This is now at a depth of 1906 ft, and shaft pockets and loading cartridges are being installed on the 1806 level. Ore from the new shaft, hoisted in 51/2 -ton Jeto bottom dump skips, is dumped into a 500-ton shaft bin, from which it is fed to a 16x30-in. gyratory crusher and conveyed 415 ft through an undersurface concrete gallery to the secondary crusher and conveying system supplying the 900-ton mill. Lead, zinc, and pyrite concentrates are floated, and the flotation tailings are cyanided after desliming. Waste from the new shaft is dumped into a 250-ton surge bin, fed from this bin to a 24-in. conveyor, and discharged into the glory hole above the block cave. The new shaft is served by a double-drum 400-hp hoist used for ore and waste; the No. 6 shaft conveys men and material To secure a cheap source of waste fill for stoping operations, a block cave area was undercut In the hanging wall near the north end of the mine above the 600 level. Waste from the block cave is drawn from any of three large drawpoints on the 600 level, and a series of hanging wall transfer raises with controls and bypasses on each level provide a fast low-cost material for fill. The block cave is worked vertically through to surface in the form of a steep-sided hole 350x250 ft and several hundred feet deep, the sides of which cave and provide fill material without any blasting. Fill is a mixture of caliche-cemented surface gravel and small particles of hanging wall schist. Level Development: An orebody 300 times as long as it is wide requires a lot of development work. Former practice consisted of driving a haulage drift about 30 ft from the ore in an andesitic footwall, a drift on the ore, and crosscuts from the haulage drift at 100-ft intervals. Crosscuts are about 90 ft long. At present, only the odd numbered levels are so developed, and on the even numbered levels only the haulage drift and crosscuts are driven. Little or no timber is used for this development. This change resulted in 20 pct reduction of development costs and 50 pet reduction of square set stoping required for removal of floor pillars. Elimination of ore drifts on alternate levels leaves

Jan 1, 1957

By R. E. Boni, G. Derge

Application of surface tension measurements has been made to molten silicates in order to determine the effect of sulphur upon the surface tensions of synthetic blast furnace slags. In melts with the same molar ratios of AI2O3 + SiO2 to the basic oxides BaO, CaO, and MgO, the surface tensions increase in the order of oxides listed. Sulphur lowers the surface tensions of the basic BaO, basic CaO, acid BaO, acid CaO, and acid MgO slags in that order; and the concentration of excess sulphur at the slag surface increases in this same order of slags. The rate and amount of desulphurization of iron by these slags is favored by a low excess surface sulphur in the slag. IN a previous paper,1 the authors discussed the applications of surface tension measurements of molten silicates to problems of metallurgical interest. Of major importance is the aid that such studies lend to forming a working concept of slag structure. Since the ability of a slag to desulphurize metal depends strongly upon its composition,2"4 fundamental information about the structural differences between various slags which contain sulphur should aid the development of better desulphurizing media. For that reason, the present investigation concerns the effect of sulphur upon the surface tensions of synthetic blast furnace slags. Experimental Procedure , The maximum bubble-pressure method was used to measure the surface tensions of synthetic blast furnace slags in the temperature range 1300° to 1600°C. The method is based upon the equation which was developed by Schrödinger5 from a consideration of the forces of hydrostatic pressure and surface tension of a liquid which oppose bubble formation when a gas is forced through a tube immersed in the liquid. where y is the surface tension between argon and slag in dynes per centimeter; g is the gravitational constant, centimeters per second2; H is the manometer reading in centimeters; s2 is the density of manometer fluid in grams per cubic centimeter; S1 is the density of the medium in grams per cubic

Jan 1, 1957

YEARS ago, when metal mining was more an adventure than a well-organized business, it was often said (with some color of truth) that unless a mine could stand bad management or mismanagement, it was not much good. Today, the natural excellencies of an ore deposit are merely a challenge to the engineers to exploit it as skillfully, as efficiently, and as profit- ably as possible. A vast amount of competent and imaginative engineering management (which includes economic analysis no less than the technologic arts of mining ore and treating it) has been required to make New Cornelia the smooth-running and successful operation that can be seen at Ajo today. New Cornelia was acquired by the Phelps Dodge Corporation when it absorbed the Calumet and Arizona Mining Company in 1931. Next to Morenci, it doubtless is the corporation&apos;s biggest asset. It in no way detracts from the achievement of Phelps Dodge engineers to say that they had an admirable ore deposit to work on. New Cornelia ore, as mined, is relatively low in grade and the deposit is by no means the largest of the Porphyries; but it has these attractive features : (1) It is peculiarly suitable for opencut mining because: (a) The overburden of waste rock lying above the ore deposit was (it has long since disappeared) almost negligible. (b) The deposit is roughly circular in horizontal section, with the horizontal dimensions four to five times as great as the maximum thickness. (Nevertheless, eventually some underground mining may be desirable.)

Jan 1, 1957

By G. K. Manning, A. R. Elsea, C. R. Simcoe

It was found that a critical boron content exists which yields the maximum boron-hardenability effect in hypoeutectoid steels, as was predicted from the mechanism proposed in a previous paper. The hardenability of boron steels with boron contents between 0.00005 and 0.0017 pct was dependent on the boron content, austenitizing temperature, quenching temperature, and austenite grain size. The effects of these variables on hardenability can be explained by the mechanism previously proposed for the boron effect. A MECHANISM has been proposed to explain the effect of boron on the hardenability of steel.&apos; The proposed mechanism assumes that transformation particles nucleate at concentrations of lattice imperfections where the energy level is high, and

Jan 1, 1957

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K&apos; = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k&apos; where k&apos; is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

When the new No. 3 Shaft is in full operation, the main hoisting duties will be in connection with the raising of: (a) ore from the various mining operations, and (b) mullock, or broken country rock, from development work in extending access to existing levels, opening up new levels, exploratory work, or sinking the shaft to greater depths.

Jan 1, 1957

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies.

Jan 1, 1957

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By Edward I. Salkovitz

RECENTLY a set of crystallographic angles for bismuth was calculated and a standard (111) projection was constructed. Since these calculations

Jan 1, 1957

By Clarence Karr

In 1955 the Federal Bureau of Mines established a low-temperature tar laboratory at its new Appalachian Experiment Station in Morgantown, W. Va. The objective of the laboratory is to investigate the yields and chemical and physical properties of tars from low-temperature carbonization of coal, to investigate means of economically upgrading these tars, and to make available to industry and the public essential data for increasing coal utilization through the establishment of a new coal-chemical industry, based on the utilization of low-temperature tars. Because of the obvious economic significance of phenols, as well as the relative ease with which they can be separated and analyzed, initial research has centered mainly around this class of tar constituents. It was realized early that no listing of phenols and their physical properties existed that included enough compounds to be practicable. The purpose of this paper is to make such a compilation available.

Jan 1, 1957