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By C. A. Stetefeldt

In May and June, 1885, I was engaged in examining the goldores of Las Minas, in the State of Vera Cruz, Mexico, with a view of finding a cheap and efficient method for extracting the gold. The following minerals could be plainly seen in the ore : magnetite, pyrites of iron, pyrites of' copper, quartz, and garnet. Neither galena nor zinc-hlende mere visible, but the ore contained a trace of lead, and in some samples of ore from the Muertos mine, 1.19 per cent. of zinc mas found. Antimony and arsenic were not present. Native gold could scarcely be seen in specimens of' the ore, and it only appeared—mainly in extremely fine particles—after pulverizing and washing. Magnetite was in every instance the most prominent mineral, its quantity varying between 43 and 67 per cent. Determinations of copper and sulphur showed that from 3.5 to 7 per cent. pyrites of copper, and from 3 to 22 per cent. pyrites of iron were present. The gold-value of the ore varied between 0.3 oz. and 0.8 oz. per ton. I do not speak of specimens, but of average samples of large quantities of ore put through the battery. In ore that had been crushed through a No. 40 screen, the gold appeared, in part, as free gold, the rest being thoroughly mixed with the magnetite and pyrites, both minerals containing about the same percentage of gold. If this free gold was brought in contact with pure quicksilver it (lid not amalgamate readily, even if the quicksilver was charged with sodium amalgam.

Jan 1, 1886

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By F. W. Bloecher

D ETERMINATION of the surface area of finely divided minerals is of interest to mineral engineers engaged in flotation, comminution, and dewatering studies. In the industrial minerals field, many materials are classified as to fineness according to their specific surface (surface area per unit weight). A method of surface area determination has been tested and used in the Richards Mineral Engineering Laboratories at M.I.T. It involves low temperature krypton adsorption measurements using the technique described by Beebe.1

Jan 3, 1951

By E. T. Peters, L. E. Tanner

In the course of a study concerned with the rnechanical behavior of the intermetallic compound CO3V, both structural observations and anomalous electrical-resistivity behavior indicated the presence of a new high-temperature phase in an alloy with the stoichiometric composition, Co-22.4 wt pet V. The evidence, which is given below, suggests that the new phase is situated between the low-temperature ordered hexagonal phase, k,1, 2and the high-temperature disordered fee solid solution, a,3 within a small range of temperature in the vicinity of 1070°C. Structural studies included X-ray diffraction analysis* and electron-transmission microscopy examination* of stoichiometric composition speci- mens homogenized for 1 hr at 1200oC and either air-cooled or water-quenched. The air-cooled specimens yielded X-ray diffraction evidence of the k phase, while electron microscopy revealed a microstructure of both heavily and moderately faulted regions as shown in Fig. 1. The high density of stacking faults (or fine twins) in region A is reminiscent of hexagonal cobalt following its allotropic transformation.4 Selected-area diffraction from this region revealed distinct superlattice reflections of the ordered hexagonal phase, as well as continuous rel-streaks which were normal to the fault planes in the micrograph. The latter is indicative of extremely small spacings between the faults.&apos; Regions such as ß were found to be only partially transformed to the k phase. Attempts to study the antiphase domain structure by either bright- or dark-field techniques were unsuccessful in these initial studies. This was due to the low intensity of the superlattice reflections arising from the closeness of the cobalt and vanadium scattering factors. Quenching Co3V from above Tc appears to suppress the formation of the k phase. Both X-ray and electron-diffraction results indicated that the disordered phase, a, was partially ordered during severe cooling and that the structure of the ordered phase was of the L12 (Cu3Au) type,6 designated here as a&apos;. As in the case of the hexagonal phase, examination of the domain structure was unsuccessful; however, significant information concerning the morphology of this condition was revealed by the appearance of dislocation arrays. In particular, it

Jan 1, 1965

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O&apos;Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2&apos;3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5&apos;6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

By C. O. Burgess, W. D. Forgeng

The results of an investigation of the ternary system iron-chromium-silicon were reported in 1936 by the present authors.l Partly for the sake of theoretical interest, and partly because of the possible commercial importance of these alloys, the present investigation was undertaken to determine the effect of some of the commoner elements likely to occur, deliberately or otherwise, in such alloys if made on a commercial scale. The elements thus added were carbon, nickel or manganese. The alloys studied were, therefore, parts of quaternary systems. This investigation was concerned primarily with the effect of these additional elements on the alpha-iron phase and the boundary between this phase region and the alpha plus sigma two-phase region. The sigma phase is a ternary solid solution based upon the compound FeCr. The work was performed mainly by X-ray methods, but a number of microscopic examinations were also made and are reported. While isolated alloys in the composition ranges studied may have been discussed in metallurgical publications, no systematic investigation of any assistance to us was found. Of the earlier work, the investigations on the iron-chromium-carbon system and on the chromium carbides by Westgren and his coworkers2&apos;3 enabled us to identify the carbide phase. Several articles appeared after the present experimental work had been completed. Lucas and Wintrup4 determined the solubility of carbon in molten iron-chromium-silicon alloys. Tofaute and his coworkers5&apos;6 have made detailed studies of the iron-chromium-carbon system, which will be referred to later. Materials and Methods Materials.—The iron, chromium and silicon used were essentially the same as those used in the investigation of the ternary system.l The

Jan 1, 1938

By C. S. Herzig

In the Engineering and Mining Journal of Jan. 27, 1900, there appeared an article by Fred T. Greene, describing a method of measuring stopes by the use of strings, a clinometer and a tape. In the early part of 1899 I had occasion to use a somewhat similar method, for the purpose of accurately ascertaining the volume of a very irregular drift connecting two mines. This drift was an important factor in a lawsuit for $150,000, in which it was necessary to determine accurately the volume originally occupied by the material extracted from the drift. While it is unnecessary to give all details of the controversy, some explanation of the conditions is required for a clear understanding of the following description. This drift was started by the a E." Co. from its workings, in about 7 ft. of ore, and headed toward the " G " property, the plan being to extract all the ore between foot- and hanging-walls, but to take out nothing but ore. As the " G." workings were approached; the ore-body became very irregular and much thinner. It was, however, very closely followed, and where the drift broke through into the " G." workings, the hole was only 11 inches high by 14 inches wide, or just about the size of a man-hole in a boiler.. Thus, this connection-drift tapered sharply; and the very irregular foot-wall sloped toward the " G." workings, and entered them at a place where the stope was only about 3 ft. high, and the ground had already commenced to cave. It may be added that the ore-body was a nearly flat deposit of lead carbonate in limestone, the ore and gangue being quite soft. I was called upon by the " G." people to make the survey

Jan 1, 1901

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965

By Kim Beattie

IN spite of the fact that in 1944 Canada experienced a decline in production of all her leading base metals-nickel, zinc, lead, and copper; despite uncured headaches in the coal-mining industry; and cheerfully ignoring a still further drop in gold, the most valuable product of her mines, which had the lowest output of any year since 1931, the Canadian miner retains the traditional optimism of miners everywhere as he looks forward to the postwar period. Some factors should keep the Canadian mining industry from being too optimistic of the coming era of peace, but the fraternity generally holds that its confident attitude towards the future is based on sound reasons. The decline in production in the Canadian mining industry last year can be almost wholly attributed to the serious shortage of labor and the difficulty in obtaining transport and supplies in remote areas. Some falling off occurred in the demand for certain strategic metals, but the diversion of gold miners, especially, without replacements being obtainable, to direct war work or allied pursuits, was certainly the principal cause of the reduced output in 1944. But that is a situation which will right itself at the close of the conflict.

Jan 1, 1945

By M. T. Hepworth, A. K. Stewart

Iron containing 0.1 pct A1 and -0.9 pct P by weight was internally oxidized in the temperature range 900° to 1300° C, where the bcc structure is stabilized by phosphorous. By measuring the depth of penetration of oxygen with time in an internally oxidized zone for an imposed surface oxygen potential, oxygen permeability was determined. The dgfusion coefficient of oxygen in iron was then calculated using known solubility data, yielding the expression: where Do is the diffusion coefficient of oxygen in bcc iron in sq cm per sec and T is temperature in OK. RECENTLY Hepworth, Smith, and Turkdoganl measured the diffusivity of oxygen in bcc iron and reported the temperature dependence of diffusivity from data determined in the a, and 6 temperature ranges. Subsequently Swisher and Turkdogan&apos; have measured the diffusivity of oxygen in fcc iron. Internal oxidation techniques were employed by these investigators and in this current study. The analysis of this technique is developed by wagner3 (presented in English by Hauffe4 and Rapp 5). In this present study bcc iron stabilized by phosphorous was used to determine oxygen diffusivity in the temperature range 900° to 1300°C. Meijerin 6 has studied oxygen permeability in this temperature range using bcc iron stabilized with 5 pct Sn. Other inves- tigators who have studied oxygen permeability in bcc iron at other temperatures are Schenck et al., 7 Bohen-kamp and Engell, 8 and Bradford. EXPERIMENTAL Electrolytic iron of 99.99 pct purity was alloyed to contain 0.897 pct P and 0.093 pct Al. The maximum weight percent phosphorous required to stabilize bcc iron between 910" and 1392°C is 0.51 pct as determined by Haughton,10 0.42 pct by Roquet and jegaden," and 0.58 pct by vogel,12 with the latter value preferred by Hansen.13 Microprobe analysis indicated that there was no segregation of the phosphorous either before or after permeability studies; therefore, the quantity of phosphorous added was assumed to be sufficient to stabilize the bcc structure. Furthermore, the permeability results of studies on this alloy agreed substantially with interpolated values from previous data on bcc iron.&apos; An ingot of the Fe-P-A1 alloy was hot-rolled to a l-in.-thick slab. Specimens were machined to dimensions: 13/8 by $ by 1/4 in. The experimental apparatus and procedure used have been described before.&apos; A constant oxygen potential was established by passing argon and hydrogen through a column of oxalic acid dihydrate, which has a water vapor pressure which is well-known as a function of temperature. Slab specimens were exposed to a gas mixture sufficiently lean in oxygen to prevent the formation of a surface oxide for predetermined temperature for selected times. The specimens were then quenched, sectioned, and examined metallo-graphically. All quenched specimens were iron-plated to provide protection from the outside sample edge during polishing. Fig. 1 shows a typical microstruc-ture for a specimen oxidized at 953°C for 48.00 hr at a water vapor-to-hydrogen pressure ratio of 0.20. DISCUSSION AND RESULTS The following equation was derived by Hepworth et al.&apos; from Wagner&apos;s kinetic expressions for internal oxidation:

Jan 1, 1969

By George C. Lipsey

FOR many years the mining of coal and other minerals occurring in sedimentary formation has been planned according to information obtained by diamond drilling. Placer mines have used churn drills for sampling and estimating deposits, and some metal mines have used the method either wholly or in part. The diamond drill method, therefore, although not entirely new, has come into more prominence in the last few years. Several large-scale developments now being planned or in the production stage have used this method in varying degree. This paper will describe the operations of the Howe Sound Exploration Co., Ltd. at Snow Lake, Manitoba, where a gold mine was developed and equipped for mining and milling wholly on the basis of diamond drilling results. The property has been in operation nearly 3 years, so that results can be compared with the estimates and assumptions made from the diamond drilling. In developing the subject it is necessary to outline as briefly as possible the normal method of mining, from discovery to production stage. Table I sets forth these various stages, the methods of financing, the percentage of total cost, and the relative time interval required for each section of the work. The plan presented in this table cannot be applied to all mining developments, but it gives a basis on which to work. In Stages 2 and 3 the investment is moderate, and if the property does not respond favorably the options or interests can be terminated. Stage 4 represents a sizeable investment, and it is more difficult to drop the property after this part of the operation is completed. Stages 2, 3, and 4 may be repeated several times by different groups or companies before Stage 5 is reached, but when Stage 5 has been started the total capital investment must be provided and there can be no turning back. It will be noted that there is a total of 116 units of investment in the overall cost if one company proceeds with Stages 2, 3, 4, and 5 in order. Stage 4, however, consumes time which is important when markets are being considered. Bringing a property into production when metal prices are low is much more difficult than when the prices are high, and if this stage can be set aside production is attained more quickly. When Stage 4 is eliminated the total becomes 86 units of cost for Stages 2, 3, and 5, but an adjustment of 14 units must be added to Stage 5. These 14 units represent the useable value of Stage 4. Thus Stage 4 represents an investment of 30 units if carried on before Stage 5, but 14 units if included with Stage 5. This is accounted for by the fact that development work can be accomplished more cheaply under Stage 5, since everything that is done is planned on a production basis with permanent services. Stage 4 must of necessity be governed by expenditures, and a great many temporary services, including housing and power plants, must be provided. The prospect shaft is a small one, and drifts,

Jan 1, 1952

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10&apos; greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.&apos; In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By J. H. Wernick, S. Geller

A number of new AB, compounds, in which A is a rare earth or yttrium atom and B is Al, Mn, Fe, Co, or Ni, having the cubic MgCu, structure (Laves phase) are reported. In most of the compounds, the interatomic distances are normal; the lanthanide contraction is observed. However, in the compounds CeB2, B = Fe, Co, Ni, Ce appears to have a valence substantially greater than three; in CeAl2, Ce appears to be trivalent. These results are interpreted as vesulting from an energetically more favorable situation for the 4f electron of Ce to be lost to the 3d band of Fe, Co, nnd Ni. Evidence for the existence of homogeneitj! ranges in these compounds is presented. THE purpose of this paper is to report on the crys-tallographic investigations of a large number of new compounds, Table I, with the MgCuz structure (cubic Laves phase). It is a part of a continuing study of the magnetic properties and structures of binary systems involving the rare earths. In a previous paper&apos; some of the magnetic properties of such systems were reported briefly. We have also reported2 a number of compounds of the CusCa type. The compounds were prepared by induction melting in Argon atmosphere of mixtures of stoichiomet-ric amounts of the constituent elements.* For most of the compounds fused alumina or silica crucibles were used as the containing vessel; graphite crucibles were used to prepare CeA12, NdAl2 and TbA12. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis-type Norelco cameras of 114.6 mm diam. The compounds AB2 belong to space group Fd3m-Ol with 8A in a): (000; 01/2 &apos;/2;3) + 000-; b % XA and 16B in dl: (000; oVa %; 3) + 5/87; % %; 7e % Vs\£>. Because the intensities of the reflections on the powder photographs of the different compounds are similar, relative intensities were computed only for DyMnz for CrKa radiation, Table 11. In the calculation of intensities, the Thomas and umeda3 atomic scattering factors, corrected for dispersion,4 were used. The agreement between observed and calculated intensities leaves little doubt that DyMnz has the MgCuz structure. Crystallographic data for the ABz compounds are given in Table JII. Twelve of these compounds have been reported by other authors. A comparison of the published results with our work is given in Table W.* ers of elements of lower purity, to peritectic reactions in some cases, and to the presence of homogeneity ranges in these alloys, so that melting losses would still result in single phase alloys. The possibility of existence of homogeneity ranges in these compounds was investigated systematically only for GdMnz. At room temperature, the solid solution range is between

Jan 1, 1961

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60&apos; bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By Cyril Wells, Robert F. Mehl

THE two earlier papers in this series1,2 presented data on the rate of diffusion of carbon and of manganese in gamma iron. Apart from their scientific interest, these [] data are needed chiefly in order to treat data on carburization, on the rate of formation of pearlite, and on the rate of austenizing in a quantitative way. 1,2,9,10 In the present investigation rates of diffusion of nickel in -?-Fe over wide temperature and concentration ranges have been determined, and the effects of carbon, of impurities, and of grain size on these rates have been studied. Claussen,3 using the data of Fry,4 has calculated the diffusion coefficient of nickel [ ] in -?-Fe as 9.2 X 10-11 sq. cm. per sec. at 1200T., but had no data from which to calculate the variation of D with concentration, temperature, and percentage of carbon. METHOD AND MATERIALS Method.-Nickel was diffused along the axis of a cylindrical specimen across a concentration gradient, concentration-penetration curves were determined and D values calculated from Grube or Matano solutions.5 Details of the method are given

Jan 1, 1941

By George C. Lipsey

FOR many years the mining of coal and other minerals occurring in sedimentary formation has been planned according to information obtained by diamond drilling. Placer mines have used churn drills for sampling and estimating deposits, and some metal mines have used the method either wholly or in part. The diamond drill method, therefore, although not entirely new, has come into more prominence in the last few years. Several large-scale developments now being planned or in the production stage have used this method in varying degree. This paper will describe the operations of the Howe Sound Exploration Co., Ltd. at Snow Lake, Manitoba, where a gold mine was developed and equipped for mining and milling wholly on the basis of diamond drilling results. The property has been in operation nearly 3 years, so that results can be compared with the estimates and assumptions made from the diamond drilling. In developing the subject it is necessary to outline as briefly as possible the normal method of mining, from discovery to production stage. Table I sets forth these various stages, the methods of financing, the percentage of total cost, and the relative time interval required for each section of the work. The plan presented in this table cannot be applied to all mining developments, but it gives a basis on which to work. In Stages 2 and 3 the investment is moderate, and if the property does not respond favorably the options or interests can be terminated. Stage 4 represents a sizeable investment, and it is more difficult to drop the property after this part of the operation is completed. Stages 2, 3, and 4 may be repeated several times by diflerent groups or companies before Stage 5 is reached, but when Stage 5 has been started the total capital investment must be provided and there can be no turning back. It will be noted that there is a total of 116 units of investment in the overall cost if one company proceeds with Stages 2, 3, 4, and 5 in order. Stage 4, however, consumes time which is important when markets are being considered. Bringing a property into production when metal prices are low is much more difficult than when the prices are high, and if this stage can be set aside production is attained more quickly. When Stage 4 is eliminated the total becomes 86 units of cost for Stages 2, 3, and 5, but an adjustment of 14 units must be added to Stage 5. These 14 units represent the useable value of Stage 4. Thus Stage 4 represents an investment of 30 units if carried on before Stage 5, but 14 units if included with Stage 5. This is accounted for by the fact that development work can be accomplished more cheaply under Stage 5, since everything that is done is planned on a production basis with permanent services. Stage 4 must of necessity be governed by expenditures, and a great many temporary services, including housing and power plants, must be provided. The prospect shaft is a small one, and drifts,

Jan 1, 1953

By George C. Lipsey

FOR many years the mining of coal and other minerals occurring in sedimentary formation has been planned according to information obtained by diamond drilling. Placer mines have used churn drills for sampling and estimating deposits, and some metal mines have used the method either wholly or in part. The diamond drill method, therefore, although not entirely new, has come into more prominence in the last few years. Several large-scale developments now being planned or in the production stage have used this method in varying degree. This paper will describe the operations of the Howe Sound Exploration Co., Ltd. at Snow Lake, Manitoba, where a gold mine was developed and equipped for mining and milling wholly on the basis of diamond drilling results. The property has been in operation nearly 3 years, so that results can be compared with the estimates and assumptions made from the diamond drilling. In developing the subject it is necessary to outline as briefly as possible the normal method of mining, from discovery to production stage. Table I sets forth these various stages, the methods of financing, the percentage of total cost, and the relative time interval required for each section of the work. The plan presented in this table cannot be applied to all mining developments, but it gives a basis on which to work. In Stages 2 and 3 the investment is moderate, and if the property does not respond favorably the options or interests can be terminated. Stage 4 represents a sizeable investment, and it is more difficult to drop the property after this part of the operation is completed. Stages 2, 3, and 4 may be repeated several times by diflerent groups or companies before Stage 5 is reached, but when Stage 5 has been started the total capital investment must be provided and there can be no turning back. It will be noted that there is a total of 116 units of investment in the overall cost if one company proceeds with Stages 2, 3, 4, and 5 in order. Stage 4, however, consumes time which is important when markets are being considered. Bringing a property into production when metal prices are low is much more difficult than when the prices are high, and if this stage can be set aside production is attained more quickly. When Stage 4 is eliminated the total becomes 86 units of cost for Stages 2, 3, and 5, but an adjustment of 14 units must be added to Stage 5. These 14 units represent the useable value of Stage 4. Thus Stage 4 represents an investment of 30 units if carried on before Stage 5, but 14 units if included with Stage 5. This is accounted for by the fact that development work can be accomplished more cheaply under Stage 5, since everything that is done is planned on a production basis with permanent services. Stage 4 must of necessity be governed by expenditures, and a great many temporary services, including housing and power plants, must be provided. The prospect shaft is a small one, and drifts,

Jan 1, 1953

By R. J. Wasilewski

Axial expansion has been determined by X-ray diffraction up to 600° to 760°C in a titanium and four high-oxygen alloys. Expansion data cannot be fitted to the usual quadratic expression and anomalies observed are believed indicative of the changes in the bonding configuration of the valence electrons. Furthermore, there is significant disagreement between data obtained on poly crystalline and single crystal powder specimens. The major disagreement occurs within the temperature range (-470°C) where both mechanical and electrical properties also show markedly anomalous behavior. X. HIS work forms part of an investigation of physical properties of pure titanium and its osolid solutiono alloys with oxygen and nitrogen. In view of the anomalies observed in both the electrical resistivity&apos; and the susceptibility behavior it was decided accurately to determine the thermal expansion behavior of the pure and alloyed a titanium. PREVIOUS WORK The axial expansion coefficients reported for pure titanium are listed below. As can be seen, there is a marked discrepancy between the axial expansion and the experimentally determined coefficients on poly crystal line material. Thus, if we take the most recently reported axial expansivities3,4 we obtain perature interval of 25o to 700°C. The experimental value reported for polycrystalline metal is, however, of the order of 9.7 x 10o6 per OC. EXPERIMENTAL I) Pure Titanium. High purity titanium powder of -325 mesh was used throughout most of this work. The only significant impurities present were the interstitials, oxygen and nitrogen, which analyzed respectively 650 and 80 ppm. The purity of the ma-

Jan 1, 1962

By L. D. Hall, S. J. Rothman

DIFFUSION coefficients of RaD (PD) and RaE (Bi) in a Bi-0.255 atomic pct Pb alloy have been measured by the methods outlined in a previous paper.&apos; The following changes were made in the experimental procedures: the bath was made up of about 400 to 500 g Bi; and no correction was made for the volume change of bismuth on melting. The data are presented in Table I and Fig. 1. A least-squares analysis of the data yielded D = (0.120 t 0.09) exp ( -9680 + 1070/RT) D- (0.0465 0.001) exp (-8100 + 466/RT). Statistical analysis of the data indicated that the activation energies are significantly different at the 50 pct level, but not at the 75 pct level, while the D values are significantly different at the 97.5 pct level, but not at the 99 pct level. The differences are thus not as clear-cut as they were for lead. However, bismuth diffuses faster than lead in high bismuth alloys as well as in lead. The high activation energies, more than twice the value calculated from viscosities, are in good agreement with the results of Grace and Derge.&apos; No data were obtained at higher temperatures because of gas bubble formation in the capillary. Acknowledgments This work was supported by the Office of Ordinance Research under contract DA-04-200-ORD-178. The authors thank 0. P. Vieria and M. Volpe for help in the experimental work.

Jan 1, 1957