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By C. D. Woodward

PrioR to 1902, the tramming of ore from the stopes to the shafts, in the Butte mines, was done by man or animal power, but the demand for greater tonnage and the need for more improved methods of tramming the ore resulted in the installation of the compressed-air locomotive in a few mines. Some of the objections to animal haulage were thus eliminated, but this locomotive was not generally adopted, because of a number of limiting features. It was superseded by the electric trolley locomotive. The early types of trolley locomotives were not satisfactory from the operators' viewpoint, but they had many economic advantages and after a number of years, in which improvements were constantly made in the structural details, they became dependable, so that the use of animals for main haulage in the mines has now been practically abandoned. There are now operating in the Butte mines of the Anaconda Copper Mining Co., 185 trolley-type locomotives, each of which has replaced five animals. It cost approximately $50 per month to keep an animal, hence the economies that resulted fully justified the expenditure of electrifying the haulage systems. The haulage conditions in this company's mines possess many advantageous features that arc not always found in underground mine workings. The drifts and crosscuts are large, approximately 5 ft. (1.5 m.) wide by 71/2 ft. (2.3 m.) high, and have curves of no less than 18 ft. (5.5 m.) radius; and the roadbeds of the drifts and crosscuts have a uniform grade of 0.5 per cent. toward the shaft, or in favor of the loaded trips. In all of the mines, except two, the track gage is 18 in. (45.7 cm.): and all tracks in the main haulageways are laid with 25-lb. (11.3 kg.) rails. The stations at the shaft are large, well-lighted, clean, and cool. The average temperature of the stations, however, is about 75" F. (24" C.), while the average temperature in some of the drifts and crosscuts is 92" I?. (33.5" C.). As the orebodies lie at varying distances from the hoisting shafts,

Jan 1, 1923

By D. Turnbull, R. E. Cech

Small particles, 10-20 microns diameter, of a 28.6 atom pct nickel, balance iron alloy, have been supercooled 186 C with respect to bulk alloy M, temperature. Particles exhibit a marked mechanical shock sensitivity while being held in a supercooled state. The tendency for shock to induce martensitic transformation appears to be a maximum at —140 to —160°. Slow cooling of particles in mechanical contact with one another results in extensive martensite formation. This is prob-ably the same effect as the catalytic effect observed in polycrystals where martensite formation in one grain induces transformation in other grains. AS a result of extensive research over the past decade on the martensitic transformation, a much better though not complete understanding of the transformation has resulted. Recent reviews by Bilby and Christian' and Kaufman and Cohen2 have

Jan 1, 1959

By W. E. Horst

During the past few years of operation at Kings Mountain, N. C., full-scale flotation has generally yielded poorer metallurgical results than those obtained in the laboratory or pilot plant. After 2 min in each size of Denver flotation machine in the spodumene rougher circuit, pilot recovery (41.7 pct) was almost three times that of the plant (13.6 pet) and about twice that of the laboratory (21.0 pet). Pilot and commercial plant data are based on continuous operation, and laboratory results on batch testing of rougher performance. The ore is a pegmatite containing spodumene, feldspar, quartz, mica, and amphibolite. Data were accumulated to evaluate the scale-up relationships between laboratory, pilot plant, and plant flotation cells. Flotation rate constants and dimensional analysis were used to define the relationship existing between flotation behavior and scale of operation.

Jan 11, 1958

By Burt C. Mariacher

The Minerals Beneficiation Division meets each year at the Annual Meeting of AIME. All members are invited and encouraged to attend. For the information of those who did not attend the meeting in Denver last February, this column presents a summary of the reports given and topics discussed. Technical Committee Coordination Consolidation of technical programs having common interest to MBD and the Extractive Metallurgy Division is proving a considerable success, both on the technical committee level-through the efforts of the MBD-EMD Coordinating Committee-and in special symposia. MBD Chairman, R. S. Shoemaker, noted that J. D. Prater will be serving as Chairman of both the MBD Chemical Processing Committee and the EMD Hydrometallurgy Committee for 1970-71. R. P. Ehrlich commented on the cooperative effort of both divisions in organizing the Copper Metallurgy Symposium held at the Denver Meeting. This effort, he said, was important to the success of the Symposium. H. R. Spedden discussed inter-Division coordination activities on the SME level. The forthcoming MBD-M&E-EMD Joint Lead-Zinc Symposium is yet another example of progress in this direction.

Jan 1, 1970

By N. Pessall, A. D. McQuillan

The phase relalionsllips in an isothernzal section of the Ti-Zr-H system at 750°Chave been investigated by measurement of hydrogen equilibrium pressures. The resulting diagram indicates that the hydride phase has an anomalously wide range of homogencity extending from 66.6 to 30 at. pct H in alloys containing about 15 al. pet Zr. Measurement of the heat of solution of hydrogen as a function of alloy composition in ß-phase alloys indicates no anomalous behavior in the region of 15 at. pet Zr, and suggests that the extensive range of homogeneity in the hydride phase at about this composition must he attributed to an enhanced stability of the, hydride phase. THE manner in which titanium and zirconium react with hydrogen and the constitutional diagrams of the two metal-hydrogen systems are qualitatively very similar,'-6 as can be seen from Fig. 1 which shows the constitutional diagrams of the two systems. Quantitatively, however, there are some differences. For example, the exothermic heat of solution of hydrogen in ß titanium is smaller than that in ß zirconium, and consequently the equilibrium hydrogen pressure of a Ti-H alloy is higher than a Zr-H alloy at the same temperature and hydrogen concentration. Other differences manifest themselves in the hydride phases which exist at high hydrogen concentrations. In the Ti-H system, above room temperature, there exists only a single hydride phase in which the metal atoms are arranged on a fee lattice, but in the zirconium system there are two hydrides, and whereas the hydride of lower hydrogen concentration has a fee structure, the higher hydride has a face-centered tetragonal structure. The tetragonal hydride retains its stability up to temperatures in excess of 450oC.7 From the foregoing, it would be expected that the constitutional diagram of the ternary Ti-Zr-H system would have a very simple form, especially as titanium and zirconium are completely miscible in both the a and ß forms.8 The present work, which consists of a study of an isothermal section of the ternary system, was carried out in order to check the assumption frequently made that the electronic structure of the two metals and the mechanism by which hydrogen is held in solution in the metals is the same for each. Although this proved largely to be true, certain inter esting and unexpected features of the ternary system emerged which must be explained before we can really say that the reactions of titanium and zirconium with hydrogen are fully understood. EXPERIMENTAL PROCEDURE The most convenient method of studying hydrogen-metal systems is by the measurement of the hydrogen pressure in equilibrium with the hydrogen dissolved in the metal as a function of hydrogen concentration and temperature. In binary systems, the results are easily interpreted in terms of alloy constitution, since two-phase regions can be recognized by the fact that the hydrogen pressure at constant temperature does not vary with the hydrogen concentration in the alloy when it is in the two-phase condition. This criterion does not apply in ternary systems, but there is usually a marked change of slope in the isothermal pressure-composition curves when a phase boundary is crossed, and with care, and a knowledge of the limiting binary systems, the phase structure of the alloys can usually be deduced. In the

Jan 1, 1962

By Joseph Hyde Pratt, Douglas B. Sterrett

Monazite is one of the minerals which, for a long time, was considered somewhat rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas arid Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals,ceriunl, lanthanum, and didymium,(Ce,La,Di)PO,. There is nearly always present a varying but small percentage of thoria, Tho2, and silicic acid, SiO2,, which are very probably united in the form of a thorium silicate, ThSiO4. Some mona-zites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent.; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellop. in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a con-choidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that werc 6 in. in length. The more perfect crystals are,-however,

Jan 1, 1910

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct ThO2,*, and the ilmenite 56 1/2 pct TiO2, whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be avail- able in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources. 1 Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations.

Jan 6, 1950

As is known to representatives on Engineering Council, the Patents Committee of Council has collaborated with the similar committee of National Research Council in developing a scheme for the improvement of the method of dealing with patents in this country. The staff of the Patent Office is itself actively engaged in this effort. Out of the report prepared by the National Research Council, and approved and adopted by Engineering Council as the report also of its Patents Committee, remedial legislation has taken form. Three hills have been introduced, known as H.R. 5011, a bill to make the Patent Office independent of the Department of the Interior or any other department, and to simplify the procedure of the Courts with reference to assessment of damages or profits for infringement of patents; H.R. 5012, a bill to establish a single Court of Patent Appeals; and H.R. 7010, a bill to increase the force and salaries in the Patent Office. Chairman Charles A. Terry, of the Patents Committee, requests that representatives of Engineering Council write to their congressmen, urging the passage of these hills and so far as convenient, request their friends to do likewise.

Jan 9, 1919

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.' That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes' developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C' is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.', ' " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann's size modulus has been found convenient.' Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-' dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J'-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-'dx\

Jan 1, 1960

By R. M. Waterstrat

The phase VPt has been reported to have a crystal structure of the B19 (AuCd) type at low temperatures.''' A recent investigation3 has indicated that this phase forms by an ordering reaction from the disordered fcc Pt(V) solid solution which is stable at high temperatures. olander4 has shown that there exists a close structural relationship between the orthorhombic B19 structure and a fcc structure possessing the L1 , (CuAu) type of atomic ordering. One may derive the B19 structure by a shear-like displacement of the atoms in the (002) plane of the ordered fcc lattice along the (010) direction through a distance equal to one eighth of the unit cell dimension, see Fig. 1, followed by an orthorhombic distor; tion of the cube axes such that a = 2.693A. h = 4.413A. and c =4.767A (estimated uncertainty 0.005A). Filings of this phase were produced by grinding a VPt alloy having the B19 structure with a diamond dental grinding disc. When these filings were subjected to X-ray diffraction examination, a pattern of a severely cold-worked fcc structure was obtained. higher solution temperature used (1200 C) or to a much lower oxygen pressure than he reported, due to transfer through many bends and tubes in his complicated apparatus. An interesting observation was made when an oxygen addition was attempted in a cylindrical sample of columbium in the cold worked condition rather than in the annealed condition. The interior of the sample re-crystallized during the oxygen addition at 900°C. The periphery, however. (1 mm) did not recrystallize. A similar sample without oxygen recrystallized throughout the entire cross section. It appears that the re-crystallization is hindered by interstitial oxygen. Presumably, the interior recrystallized before appreciable oxygen could diffuse into the core. This work was supported by the United States Atomic Energy Commission. When the filings were annealed in a high vacuum furnace for 15 min at 110O0C, however. they returned to the B19 structure perhaps as a result of reordering. Subsequent less-severe cold-working of these filings by grinding in a hardened steel mortar and pestle at room temperature produced a transformation into a cold-worked L1, structure which was slightly tetragonal. Thus it appears that the degree of deformation may influence the final structure. Considerable line-broadening was observed in X-ray diffraction patterns obtained from the cold-worked filings and therefore no attempt was made to obtain accurate lattice parameters. Vacuum annealing treatments at 1100'C intended

Jan 1, 1970

By Charles H. Hopkins, J. M. Lohr

A commercial development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common types of glass under consideration varies from 2.7 to 10.4 X 10-6 per degree Centigrade, over the range 20" to 400' C. For reference, the t,hermal expansion curves of several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1939

By Charles H. Hopkins, J. M. Lohr

A commercial development requiring a suitable alloy or alloys for sealing into various grades of glass made it desirable to have a more exact knowledge of the expansion characteristics of the nickel-iron alloys than appeared in the published literature. The expansion of the more common types of glass under consideration varies from 2.7 to 10.4 X 10-6 per degree Centigrade, over the range 20" to 400' C. For reference, the t,hermal expansion curves of several types of glass used for sealing by the lamp and tube industries are given (Figs. 1 and 2). This paper covers a detailed investigation of the thermal expansion of a series of nickel-iron alloys in which the nickel content varies from 30 to 70 per cent. Particular stress is laid on the alloys that contain between 40 and 55 per cent Ni.

Jan 1, 1939

By M. T. Hepworth, R. Schuhmann

Hydrogen solubility measurements were made on a series of Ti-O alloys, and a portion of the 800°C isotherm for the Ti-O-H system was determined. Activities of oxygen and titanium were calculated from the experimentally measured activities of hydrogen, using ternary Gibbs-Duhem integrations. The data were extrapolated to obtain thermo-dynamic properties of binary Ti-O solutions. The thermodynamic properties of a Ti-0 solid solutions thus determined were compared with properties predicted from interstitial models. The Gibbs-Duhem equation, long used to calculate activities in binary systems, has been extended. recently to ternary systems.1"3 When the activity of one component in a ternary system is known as a function of composition, the activities of the other two components can be calculated from that of the first by an integration procedure, provided certain restrictions are observed on the path of integration. Often the activity of one component in a ternary system can be measured readily, while the activities of the other two components are difficult to measure. Gibbs-Duhem calculations are especially applicable to such systems. The further possibility arises of developing a new and indirect approach to activity measurement in binary systems. The proposed new method for binary systems consists of adding varying amounts of a third component whose thermodynamic behavior is easily measured. The activity of this added component is determined experimentally as a function of composition. Then the activities of the two components of the original binary system are calculated by Gibbs-Duhem integrations and extrapolations. For the work to be described in this paper, the Ti-0-H system was selected as a promising system for evaluating this approach. Investigations of the Ti-H system have shown that the activity of hydrogen can be measured precisely with little difficulty. Pure titanium transforms from a low-temperature a form (hcp) to a higher-temperature /3 firm (bcc) at 882.5"~ The phase transformation occurs in a temperature range where hydrogen pressures are easily measured. Also, the diffusivity of hydrogen at temperatures above 600" or 700"~ is large enough that equilibrium can be reached within a reasonable time.

Jan 1, 1962

By Carl Floe

A NUMBER of proposals have been made for the hydrometallurgical recovery of copper from flotation concentrates, but as yet no process has been developed that has demonstrated an ability to compete with the present smelting methods under ordinary conditions. The treat-ment of copper concentrates by hydrometallurgical methods is in general similar to that used in the present electrolytic zinc process and involves roasting, leaching with H2S04 solution, separation of solutions, control of impurities and electrodeposition. While many of these steps are simpler and more readily carried out for copper than for zinc, a number of inherent difficulties have prevented the general adoption of the process. To compete with smelting, the following problems must still be con-fronted, although many solutions for their have been proposed: (1) con-duction of the roast in such a way that leaching will give an extraction of copper comparable to that obtained by smelting; (2) regulation of the ferric iron content of the solutions during electrolysis; (3) disposal of the excess acid regenerated from the sulphates formed in roasting; (4) eco-nomical recovery of the precious metals from the leach residues. The roasting problem is largely one of preventing the formation of copper ferrites, CuO.Fe2O, and Cu20.Fe2O3, which are quite insoluble in dilute sulphuric acid. These ferrites are apparently formed' to a small extent even at low temperatures and above 650° C. their formation is rapid1. While it is possible to carry out laboratory roasts in such a way that less than 5 per cent of the total copper is present in the insoluble ferrite form, a closer temperature control is required than can readily be obtained in industrial furnaces. The flash" roasting effects and consequent high temperatures that occur as the calcine falls from hearth to hearth in the ordinary multiple-hearth roaster are probably largely responsible for the inevitable formation of some ferrites. The result is that in a commercial plant the extraction of copper would not average more than 90 per cent in a single 10 per cent H2SO4 leach. This is

Jan 1, 1937

By G. I. Madden, L. H. Van Vlack

WhEN basic refractories which contain peri-clase, MgO, are used in steel furnaces, they are altered by iron oxide to form magnesiowiistite, (Mg,Fe)O, and an iron-rich magnesioferrite, (Mg,Fe)Fe2O4. Silica, which is usually present, produces a silicate liquid that surrounds the solid phases. The individual crystalline grains of the above two solid phases grow at elevated temperatures. Previous papersL" showed that, if either periclase or magnesiowiistite is present as the only solid phase, its grain size increases in proportion to temperature and in proportion to the square root of time; the growth rate is reduced slightly if the amount of silicate liquid is increased. Similar results have been observed for iron-rich magnesioferrite.3 To determine the effect of the presence of two solid phases on the rate of grain growth, micro-structural studies have been made on samples containing both magnesiowustite and magnesioferrite. The experimental procedure was the same as that followed in the previous studies of this type.'12 Briefly, this included determination of compositions from the available phase relationships4 that would produce the two phases of interest at the firing temperature and using reagent-grade raw materials to prepare mixtures of these compositions. The mixtures were pressed into pellet-size samples and then fired at the desired time and temperature. The samples were water-quenched to preserve the microstructure present at the firing temperature. Standard reflected-light metallographic techniques were used for sample examination and sample analysis. Grain sizes were determined by measuring the mean diameter of a number of randomly selected grains in a two-dimensional microsection. A large cross section of the sample was covered to prevent biased data resulting from such effects as localized differences in the radius of curvature of the crystal grains. Examination indicates that grain growth is restricted when more than one solid phase is present. This is illustrated in Fig. 1 for: (a) magnesiowustite plus a silicate liquid; (b) magnesioferrite plus a silicate liquid; and (c) magnesiowiistite and magnesioferrite plus a silicate liquid. Fig. 2 plots the

Jan 1, 1964

By C. R. Hocott

The distribution and movement of fluids in oil reservoirs are influenced to a great extent by capillary forces, which depend upon the size and shape of the pores in the reservoir rock, the surface characteristics of the rock, and the interfacial tension between the fluid phases. This paper presents the results of an investigation of the interfacial tension between salt water and crude oil containing dissolved gas under reservoir conditions. Apparatus and Procedure In the preliminary phases of this investigation, it was found that a scum formed at the oil-water interface, which made measurement of interfacial tension by either the ring or capillary rise methods unreliable. Accordingly, the drop-weight method, in which a fresh interface is continuously formed, was selected. In this method, a tip through which drops of one fluid can be expelled is immersed in a second fluid. At the instant that the drop becomes large enough to fall, the gravitational force tending to pull away the drop exactly balances the interfacial force tending to hold it. From the size of the drop, the dimensions of the tip, and the density of the two fluid phases, the interfacial tension may be calculated. The apparatus consists of a circulating pump for bringing the oil to equilibrium with gas at the desired pressure, a displacement pump for forming the drops, an interfacial tension cell in which the drops are formed, and a density cell to determine the density of the oil. The density of the water is determined separately in another apparatus. A flow diagram of the assembled equipment is shown in Fig. 1. The interfacial tension cell contains a stainless-steel dropping tip suspended from the top and extending below the surface of the oil. The tip is a cylindrical rod with a small hole in the center through which the water was forced to form the drop on the lower face. The walls of the tip were highly polished, to prevent the water on the tip from creeping up the side and increasing the effective diameter. The face of the tip, how-

Jan 1, 1939

By C. R. Hocott

The distribution and movement of fluids in oil reservoirs are influenced to a great extent by capillary forces, which depend upon the size and shape of the pores in the reservoir rock, the surface characteristics of the rock, and the interfacial tension between the fluid phases. This paper presents the results of an investigation of the interfacial tension between salt water and crude oil containing dissolved gas under reservoir conditions. Apparatus and Procedure In the preliminary phases of this investigation, it was found that a scum formed at the oil-water interface, which made measurement of interfacial tension by either the ring or capillary rise methods unreliable. Accordingly, the drop-weight method, in which a fresh interface is continuously formed, was selected. In this method, a tip through which drops of one fluid can be expelled is immersed in a second fluid. At the instant that the drop becomes large enough to fall, the gravitational force tending to pull away the drop exactly balances the interfacial force tending to hold it. From the size of the drop, the dimensions of the tip, and the density of the two fluid phases, the interfacial tension may be calculated. The apparatus consists of a circulating pump for bringing the oil to equilibrium with gas at the desired pressure, a displacement pump for forming the drops, an interfacial tension cell in which the drops are formed, and a density cell to determine the density of the oil. The density of the water is determined separately in another apparatus. A flow diagram of the assembled equipment is shown in Fig. 1. The interfacial tension cell contains a stainless-steel dropping tip suspended from the top and extending below the surface of the oil. The tip is a cylindrical rod with a small hole in the center through which the water was forced to form the drop on the lower face. The walls of the tip were highly polished, to prevent the water on the tip from creeping up the side and increasing the effective diameter. The face of the tip, how-

Jan 1, 1939

By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach deposits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits. The principal titanium mineral used is ilmenite, but as soon as that mineral began to be sought as a titanium ore, it was obvious that there are ilmenites and ilmenites. Textbook ilmenite should have the composition FeOTiO2 and should analyze 52.6 pct TiO2 and 36.8 pct iron as Fe. The Indian ilmenite, for almost a generation the standard ore for manufacturing pigment in the U. S., was found to analyze about 60 pct TiO, and only 24 pct. Fe, and most of the iron is in the ferric condition. The whole process of pigment manufacture in the U. S. was built up on the use of a raw material of that grade, and the American chemical engineers who operate the pigment plants shuddered at the thought of using a rock ilmenite with 45 pct or so of TiO, and nearly 40 pct Fe. Intensive search was made around the world to find other deposits of rich black sand, like the Indian beaches, but although a few were found, there was some objectionable feature about each. A deposit in Senegal, south of Dakar (Fig. 7), was worked for a while, but an organic coating on the grains made attack by acid difficult. Modern practice would have included a scrubbing operation, in a caustic soda bath, to eliminate the organic coating. Brazilian deposits were numerous, but individually small, and shipping from them difficult. Deposits on the east coast of Ceylon had many attractive features, but the ilmenite analyzed only 54 pct TiO2 and could have been used only with a penalty. Sand deposits with 2 pct ilmenite, like those now worked in Florida, would not have been considered commercial ore, even if they had been known at that time. Most rock ilmenites are associated or mixed with hematite or magnetite, which accounts for the lower titanium and higher iron values than in the sand ilmenites. The Norwegians, English, and Germans, with cheap Norwegian rock ore at hand, learned to install in their pigment plants adequate capacity on the black side, as it is calltd, and counterbalanced the extra cost of plant, and larger amount of acid used, by the lower cost of ore. When World War II arrived, two of the largest pigment manufacturers in the U. S. had to learn how to use the Adirondack ilmenite, but one of them very gladly went back to sand ores when the Florida deposits came into large-scale production after the war. The other continues to use Adirondack ilmenite and finds it commercially attractive to do so. Rutile is not a raw material for titanium pigment manufacture by the sulfate process, since it is insoluble in sulfuric acid. In addition to its small consumption in chemicals and ceramics it began to be used in quantity in welding rod coatings. With the outbreak of World War 11, and the tremendous need for welding rods in shipbuilding and other structural steel construction, rutile suddenly became in heavy demand. The sand deposits on the eastern shore of Australia (Fig. 8A) which had been worked in a small way since 1934 were brought into production, and some stream placers in Brazil were worked and rutile concentrates shipped to American

Jan 1, 1960

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By Thomas P. Oxford, Leslie G. Bromwell

The waste clay slurry produced during beneficiation of Florida phosphate ore presents a major environmental problem. The large volume of waste requires impoundment in above-ground disposal areas surrounded by earthen dams. As the result of a comprehensive research effort, three approaches to improving clay dewatering involving admixing of sand tailings have been developed. These provide satisfactory performance and appear to be compatible with the technological and economic constraints of the industry. Means of determining waste clay characteristics and analyzing mining waste disposal situations by computer simulation have been devised in support of the planning and field testing effort. Detailed examples demonstrating the applicability of the computer programs are presented.

Jan 1, 1980