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By E. S. Lenker, H. J. Van Hook

A complete swies of solid solutions has been found between the compounds InAs and GaAs Below the solidus. The melting relations determined by differential thermal and static quenching technzques, indicate that the liquidus and solidus are of the simple ascendant type. No evidence of unmixing of the homogeneous solid solutions was observed at sub-solidus temperatures. A quenching method for locnting the solidus, using X-ray diffraction techniques, is described in some detail. THE semi-conducting properties of compounds formed by various combinations of the less familiar intermetallic elements have created an increasing interest in the phase relations in systems involving these elements. The complete phase diagram of such a system, containing a compound of special interest, will often provide information as to the most favorable conditions for preparing large crystals from a melt, as well as specifying the temperature stability of the crystalline phase or phases produced. In view of the current importance of gallium arsenide in semiconductor research and of the structural similarities of indium arsenide, it was thought that the complete phase relations of the system InAs-GaAs should be investigated. Previous work on the system Ga-As by Koster and homa' and on In-As by Liu and peretti2 has shown that GaAs and InAs are the only compounds formed, having melting points of 1238° and 942°C, respectively. In a survey of various systems of elements from groups IIIb and Vb, spengler3 also re- Mines Ltd., for his continuing encouragement and for permission to publish the results of this work. ports complete miscibility of gallium, indium, and arsenic in the liquid state. In a partial investigation of the InAs-GaAs system, Woolley and smith4 found extensive solid solution throughout the alloy range. Their subsolidus work, however, was inconclusive at temperatures below 900" and they did not determine the liquidus relationships of the system. PRESENT INVESTIGATION The starting materials used were high-purity gallium, indium, and arsenic. The method of preparation of the compounds follows that devised by M. Shafer and is described in detail in a paper by Shafer and eiser.' The end-member compounds, GaAs and InAs, were first prepared by reaction of the elements in the desired proportions in evacuated silica glass vials. The vials were rotated in a furnace as the temperature was slowly raised to insure rapid and complete reaction at low temperatures. Thereafter the starting materials, GaAs and InAs, were melted by heating the sealed vials to 1300" and 1000°C, respectively; the vials in this case were filled as completely as possible to keep the vapor space small and thereby minimize the loss of arsenic to the vapor phase. Ten binary mixtures of these compounds were then prepared by reaction of the powdered material in the solid state just below solidus temperatures. At 900C preparations containing 3, 5, 8, 10, 25, 35, 50, and 75 mol pct GaAs were found to be single homogeneous phases, indicating a complete series of solid solutions between GaAs and InAs. Moreover, it was discovered that the homogeneity of any crystalline binary preparation could be very accurately checked by X-ray diffraction because of the large differences in unit cell dimensions of the end membe5s. The cubic lattice constant ofor GaAs is a = 5.652A and that of InAs is a = 6.061A

Jan 1, 1963

By M. H. Pilkuhn, H. Rupprecht

The junction luminescence of GaAsxP1-x diodes containing up to 47 pct Gap was studied. Diodes were prepared by diffusing zinc into n-type material which was eithw boat- or vapor-gvown. Observations concerning the energy and the line shape of the spontaneous emission are presented and discussed; in particular the influence of inhomogeneous phosphorus distribution is considered. The role of reabsorption of the junction radiation is pointed out. With increasing current, the peak emission shifts to higher enwgy. This is alm true in cases where slow line narrowing occurs simultaneously. The length dependence of the threshold current density for lasing at 77 °K was examined for lasers made from the same material. It was found that longer lasers have lower threshold curvent densities, Estimates of the characteristic laser losses are given. Data concwning the range of Gap concentration in which stimulated emission was observed are presented. FORWARD-BIASED p-n junctions in mixed alloys of GaAsxPl-, emit light whose wave length depenfs on the composition of the alloy ranging from 8400A (x = 1) to 5350A (x = 0) at 77°K. Laser action in vapor-grown material was first reported by Holonyak and evacqua,' and in boat-grown material by Ainslie, Pilkuhn, and Rupprecht.' In both cases this was observed for low Gap concentration where GaAs,Pl-, is still a "direct" semiconductor with the lowest conductance-band minimum at k = 0 and a subsidiary minimum in the [loo] direction. As the Gap concentration is increased, the subsidiary [loo] minimum in the conduction band is lowered and finally becomes the lowest minimum for Gap concentrations above 50 pt,3 making the alloy an ''indirect" semiconductor. It is of interest to determine up to which Gap concentration stimulated emission can be observed. EXPERIMENTAL Boat-grown material was prepared by N. Ainslie of IBM by horizontal Bridgman technique. The material was n type and silicon-doped up to a concentration of 10'' cm-'. Vapor-grown material was made by E. Hull of IBM or received from Merck & Co. Diodes were fabricated in a similar manner as in the case of GaAs by zinc diffusion. Details about the diffusion can be found in a later paper.4 All diodes were of Fabry-Perot structure with two parallel sides cleaved and the other two sides sawed. Their width ranged from 50 to 150 p and their length from 50 to 700 p. RESULTS AND DISCUSSION Spectral Distributions. A typical display of the junction luminescence of a GaAsxPl-, diode is shown in Fig. 1. The liquid-nitrogen and room-temperature curves which were taken at a very low current (25 ma dc) show a relatively sharp high-energy emission which is band-edge radiation. They also show a broad low-energy emission which is due to transitions to deep impurity levels. This latter emission line may have different shapes and positions depending on the nature of the material. It can sometimes be quite near the band gap giving rise to "bumps" in the high-energy line. The results presented in this paper will be concerned only with the high-energy emission which becomes more intense relative to the low-energy emission when the current is increased and the temperature is lowered.

Jan 1, 1964

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'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 S. Leber

Pole figures and pole distributions were used for the quantitative detevinination of the preferred orientations in swaged tungsten rods and the effect of subsequent wire drawing on the texture. In the swaged rod, the preferred orientation could best be described as a pseudo (111-112) [110] cylindrical texture. A secondary component was assigned the indices (110) [001]. Further reduction by swaging retained these cylindrical textures. Wire drawing caused lattice rotations about the wire axis, converting the cylindrical texture into a normal fiber texture. The conversion was initiated and proceeded lnost rapidly in the center of the wire. The (110) /001] component was converted into a (110) fiber texture by wire drawing. The effective rotations were about axes contained in the lransverse plane. The preferred orientation associated with tungsten wire usually has been assumed to consist of a (110) fiber texture. This implies rotational randomness around the wire axis. Leber1 has shown that rotation about the wire axis may be restricted resulting in a preferred orientation designated as a cylindrical texture. Specific crystal planes tended to remain aligned parallel to the wire surface. This texture seemed to be the result of the swaging operation used in the intermediate stages of fabrication. Bhandary and cullity2 detected similar textures in swaged iron wires. Peck and Thomas3 suggested that the preferential alignment of crystal planes parallel to the wire surface was the result of tangential flow, characteristic of swaging. Wire drawing, following swaging, twisted the crystals about axes parallel to the wire axis, converting the cylindrical texture into a normal fiber texture.4 In this investigation, quantitative techniques were used to more accurately characterize the cylindrical texture and to study its conversion into a normal fiber texture. PROCEDURE The material investigated was lamp-quality tungsten. Three ingots were rod-rolled and swaged to 112 mils diameter, and were then drawn to 10-mil wire. Samples were obtained after each drawing pass. (110) and (200) pole figures were obtained from samples prepared as shown in Fig. 1. To form the sample shown in Fig. l(a), l-in. lengths of wire were glued side by side to form a l-in. square. The composite was ground and electropolished to form a diametral reference surface. For certain specific tests, samples were prepared as shown in Fig. l(b). This composite was made from 10-mil-thick strips prepared by grinding on parallel longitudinal planes. The polished reference surface in this case was, in essence, the wire surface. The two forms of samples [~igs. l(a) and l(b)] were related by a 90-deg rotation around the wire axis. Because of ease in preparation, most data was obtained from the diametral samples. The X-ray data were obtained using a Siemen's pole-figure goniometer. These data were not corrected for absorption or defocusing effects, since only the angular locations of the intensity maxima were of interest. Regions of the pole figure more than 80 deg from the center were not investigated. Partial monochromatization was achieved by the use of unfiltered copper radiation and a krypton-filled proportional counter. No evidence of spurious white radiation effects5 could be detected. Therefore, more elaborate X-ray techniques were not required. Intensity levels were chosen to show all pertinent details of the orientation distributions. The reference plane for the pole figures was the diametral section. The orthogonal reference directions, shown in Fig. 1, were the wire axis, the radial axis per-

Jan 1, 1965

By J. G. Kura, P. D. Frost, L. W. Eastwood

THE preparation and general properties of mag-nesium-lithium base alloys have been described in earlier papers.l,2 Lithium forms solid solutions with pure magnesium, lowers its density, and improves its formability. The improved isotropy and better formability of these alloys are attributed to the ability of lithium to convert the magnesium lattice from hexagonal (alpha phase) to body-centered-cubic (beta phase) structure. This change in structure is, however, accompanied by some limitations which make it difficult, if not impossible, to combine all the desirable properties in one composition. The most important of these limitations is the tendency of the high-strength alloys to overage and lose strength at temperatures of the order of 150" to 200°F. A study was made of the effects of composition and heat treatment on the age-hardening character- istics of the alloys. Stability of properties was determined by hardness and tensile testing of the alloys at room temperature after various periods of exposure to elevated temperatures. Precipitation-hardening curves are shown for a number of magnesium-lithium-zinc alloys in fig. 1. All the alloys were solution treated at 700°F and aged at 200°F. The reason for using the drastic quench, toluene at —105°F, was to reduce the rapid precipitation of the hardening phase which takes place at room temperature. Previous experience has shown that a hardness of about 90 to 95 Rockwell E is indicative of yield strengths in the range of 35,000 to 40,000 psi. This is a desirable strength level for magnesium-lithium base alloys with specific gravities of the order of 1.65 or less. Although the hardness level is raised by large zinc contents, a corresponding decrease in the cold formability of these alloys occurs with increasing zinc content. Thus, alloys containing up to about 10 pct Zn and having hardnesses of the order of 70 to 75 Rockwell E may be bent over a very small radius; however, the 16 pct Zn alloy requires a bend radius of more than 8T. The hardness relationships illustrated in fig. 1 can be explained by the partial phase diagram shown in fig. 2. The zinc-free magnesium-lithium alloys are entirely body-centered cubic (100 pct beta phase) when the lithium content of the binary is 10.3 pct or higher. When zinc is added, the boundary between the beta and alpha-plus-beta fields at 700°F is shifted to lower lithium contents. In addition, the solubility of zinc at 700°F decreases with decreasing lithium content. It is shown by a study of micro-structures that the limit of solid solubility of zinc in the 6Mg/Li* matrix at 700°F is about 19 pct. It is believed from a study of the aging curves that this limit is about 2 to 3 pct at 200°F. Zinc additions up to about 2 pct increase the hardness and strength of the magnesium-lithium base solid solution. Larger additions of zinc effect further hardness increases, but precipitate during prolonged aging at 200°F. Alloys having 14 to 20 pct Zn precipitation harden extremely rapidly during quenching, even when quenched in toluene at —105° F. The high-zinc alloys overage at 200°F but are capable of maintaining reasonably high hardnesses for periods up to 1000 hr.

Jan 1, 1951

By Nicholas J. Grant, Rolf Nordheim, Bill C. Gissen

The system Cb-Re was examined in detail utilizing pure metals, careful melting techniques, and heat treatments. Metallographic and X-my methods were utilized for phase identification. In addition to soli-dus determinations, the composition limits and mode of formation of the intermetallic compounds 0 and X were determined. The binary constitution diagram Cb-Re has been the subject of a number of investigations.'-7 Two intermetallic phases have been described and tentative diagrams have been proposed. It was the aim of this investigation to obtain a complete and more accurate diagram through the use of purer alloys and improved techniques. The diagram worked out by Knapton7 was published after our experiments were concluded. EXPERIMENTAL METHODS The starting materials were Re powder of 99.95 pct purity, supplied by the Chase Brass and Copper Co., and Cb rondelles of 99.6 pct purity, supplied by the Electro Metallurgical Co. Typical analyses are given in Table I. The alloys were prepared from compacted Re powder and Cb rondelles; for critical compositions master alloys were used. The melts varied from 5 to 50 g and were melted nonconsumably in an Heraeus arc furnace, under ti-tanium-gettered laboratory grade argon. It was necessary to invert the buttons and remelt, followed by crushing and further remeltings, the number of which depended on the nature of the fracture of the alloy. The weight of each alloy was carefully checked after each melting operation. It was found that significant weight losses occurred only when loose Re powder was used. These losses amounted to a maximum of 3 wt pct in such instances, but did not occur after the charge was once molten, regardless of the composition. Typical loss of weight after 4 remelts, including crushing, amounted to 0.2 wt pct. Oxygen pickup during successive melting cycles did not appear to be significant, since the weight gain values never exceeded 0.01 wt pct. Control of the composition of the alloys was not too difficult; however, the problem of homogenization was a far greater one. Optimum alloying conditions were finally achieved by a combination of master alloy production and repeated crushing and remelting cycles. The compositions of the alloys utilized to determine the constitution diagram are listed in Table 11. The weight balance method was used ultimately as the sole analytical method, since repeated checks indicated that it was accurate to 0.2 pct, if the weight losses were small. The results were double-checked by a metallographic study of the homogeneity of the samples, since this was presumed to be the more serious factor. Heat treatments at 1200°C or lower were accomplished by sealing the specimens in Vycor tubes, heating in a Globar furnace, followed by air cooling. This was considered to be an adequate quench because of the very low temperatures involved. For temperatures of 1200" to 1900°, alloys were homogenized and heat treated in a tungsten-filament resistance vacuum furnace. From 1900" to 2750" a tantalum-tube resistance furnace was utilized, operating under a vacuum of 105 mm Hg. The temperature measurements up to 1200" were made by means of platinum-platinum 10 pct Rh thermocouples, with an accuracy of 5°C. For temperature measurements greater than 1200°C, optical pyrometers were used. They were calibrated against a standardized instru-

Jan 1, 1962

By L. B. Gittinger

Sulfur is a nonmetallic element widely distributed in nature. It constitutes 0.06% of the earth's crust but only a very small portion occurs in sufficiently concentrated amounts to justify mining. Sulfur occurs in practically all animal and plant life. It constitutes approximately 0.09% of the elements in the oceans; it has been found in meteorites. Sulfur was known and used by man before recorded history. The American Chemical Society approved spelling for the element is sulfur. The English spelling sulphur is used commercially in the United States. In ancient times, sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Sulfur is found naturally in the elemental form in subsurface deposits associated with gypsum and anhydrite in salt domes and sedimentary formations in evaporite basins and in solfatara-type deposits associated with volcanoes and mineral springs. Sulfur occurs also in molecular combination in ferrous sulfides (pyrites and pyrrhotite) and nonferrous sulfides (copper, lead, zinc, and nickel), and in mineral sulfates (gypsum and anhydrite); as hydrogen sulfide contaminant in natural gas; as organic compounds in crude oil and tar sands; and as pyrite and organic compounds in coal and oil shales. Sulfur resources are abundant and exist throughout the world but the extent to which they can be classified as reserves is greatly circumscribed by prevailing prices and technology. Estimates of world sulfur reserves are compiled by the U.S. Bureau of Mines. A compilation of reserves by area and source of sulfur published in 1970 and presented here as [Table 1] totaled 2.47 billion tons (Lewis, 1970). The effect of the decline in prices which has occurred since the earlier estimate is dramatically illustrated by the 1972 estimate of the U.S. Dept. of the Interior which shows world sulfur reserves of only 1.2 billion tons (Anon., 1972d). Sulfur is produced commercially from one or more sources in nearly 70 countries of the world. World production of sulfur in all forms totaled 41.6 million tons in 1971. (Sulfur statistics given in this chapter are long tons.) Native deposits, sulfides and oil and gas contributed, respectively, 31, 41, and 25% of world production (Table 2). Of the sulfur produced from native deposits, salt domes accounted for 54% and evaporite basin deposits, 44%. Volcanic deposits are of little significance except for local consumption. The past two decades have seen important shifts in the world's sulfur sources. In 1950, native deposits and sulfides each supplied about one-half of the world's production. During the 1950s, sulfur recovered from oil and natural gas grew rapidly, representing about 10% of the total by 1960. Since then, the petroleum industry has continued to increase its relative importance as a source of sulfur, representing more than 30% at 1972 year-end. Sulfur is generally classified as elemental or nonelemental for statistical purposes. Elemental sulfur is sulfur produced in the pure, uncombined form. It includes production from native deposits, as well as that recovered in the elemental form from oil and natural gas or other sulfur-bearing materials. When produced from other than native deposits, it is generally referred to as recovered elemental sulfur. Nonelemental sulfur is that which is utilized commercially in molecular combination with other elements, such as sulfides or sulfates. Elemental sulfur is being produced from salt dome deposits in the Gulf Coast region of the United States and the Isthmus of Tehuantepec in Mexico, and from evaporite basin deposits in west Texas, Poland, Sicily,

Jan 1, 1975

By P. S. Kotva

Dislocation substructures in superalloy matrices of varyzng co)npositions have been studied. In general, it has been found that the alloys can be classified into ''high", ''medium", and "low" stacking fault energy classes based on the type of dislocation substructure observed in the matrix and that the substructure can be correlated to the stacking fault energy. The effect of different types of dislocation substructure and dislocation reactions on the intragranulur precipitation of carbide phases has been studied. In a Ni-Cv-Mo-Fe matrix, precipitation of MC carbides in association with stacking faults has been observed. In most superalloys, solid-solution strengthening and precipitation hardening are the chief mechanisms employed to achieve strength. The latter contribution to strength is usually achieved by the precipitation of / in certain wrought alloys. Insufficient attention has been given to the problem of obtaining strength in su-peralloys by controlling precipitation of carbides on imperfections within the matrix. The present work was undertaken to investigate the dislocation substructure in various superalloy matrices, to study the effect of such substructure on subsequent precipitation of carbides in the matrix, and to investigate whether certain modes of precipitation of carbide phases found in austenitic stainless steels2"4'6 would occur in nickel-base alloy matrices with dislocation substructures of the same type as those found in austenitic steels. 1) EXPERIMENTAL TECHNIQUES Five-pound heats of the various alloy compositions reported here were vacuum-cast. The ingots were given light deformation by rolling to break up the as-cast structure and then homogenized for 24 hr. HASTELLOY alloy X (nominal composition: Ni-2OCr-17Fe-8Mo-0.05C) was homogenized at 2150°F and In-cone1 625 (nominal composition: Ni-20Cr-5Fe-8Mo-3.5Cb-0.05C) was homogenized at 2280°F. Fabrication of 0.004-in. sheet was achieved by cold rolling with intermediate annealing treatments being carried out at the same temperature as those used for homogeniza-tion. Each solution anneal was followed by quenching. The aim of this procedure was to redissolve as much of the primary carbide phase as possible. Samples of the 0.004-in. sheet were cut and encapsulated in quartz capsules and then heat-treated in the tube furnaces. Thin foils were prepared using an ethanol-10 pct perchloric acid bath at 32°F and at a voltage of 22 v. A "window" technique was employed. Observations were made on a JEM-7 electron microscope operating at 100 kv. 2) EXPERIMENTAL RESULTS a) Types of Dislocation Substructure. Fig. 1 shows a schematic correlation between stacking fault energy, SFE, and the type of dislocation substructure observed in various matrices of nickel- and cobalt-base alloys. A precise quantitative determination of stacking fault energy is not implied in the figure but the correlation between stacking fault energy and the type of dislocation substructure obtained allows alloys to be divided into three classes in analogy with the classification employed by Swann and ~uttin~' for binary alloys of copper. Class I alloys are associated with a "high" SFE and show a cellular substructure of dislocations as typified by the micrograph of a thin foil of pure nickel deformed 4 pct at room temperature in Fig. 2. With decreasing SFE the tendency toward cell formation is lessened and dislocations tend to be arranged in coplanar groupings. Examples of this class of alloys with "medium" SFE are provided by the mi-crostructure of solution-heat-treated, quenched, and deformed thin foils of HASTELLOY alloy X, "Waspaloy" (prior to any aging), and Inconel 625. Fig. 3 shows a thin-foil micrograph of an alloy of Inconel 625 composition, solution-heat-treated, quenched, and deformed 5 pct at room temperatures. No evidence of any cell structure can be obtained in materials of "medium" stacking fault energy, Fig. 3, even after severe deformation. The stacking fault energy of the alloy shown in Fig. 3 is, however, not low enough to make the dissociation of dislocations visually obvious. As stacking fault energy decreases further, with successive addition of solute in the matrix, there is an increased tendency toward dissociation of dislocations and cross slip becomes progressively more difficult. Eventually, when the stacking fault energy is "low" enough, complete dissociation of dislocations is seen to occur as shown in Figs.

Jan 1, 1969

By N. J. Grant, D. S. Bloom

N recent reports, Sully' and Beck and coworkers' I have advanced hypotheses concerning the formation of the phase. Both of these hypotheses are based on Pauling's theories of the electronic configuration of the elements of the first transition group. Sully considered that the number of electrons which can be absorbed in filling electron "holes" is the factor which determines whether or not the structure can form. Beck suggested that the presence of a certain concentration of electron "holes" is the controlling value. It can be shown that a similar criterion can be developed without making reference to Pauling's theories. Table I shows the elements of the first transition group and the incidence of the a structure in the binary systems of these elements according to the data presently available. Also appended is the number of electrons considered to exist in the 3d-4s levels of these elements. If the atomic percentages for the phase are listed as shown in Table 11, and if the number of electrons in the 3d-4s levels per atom is calculated for the a boundary values, the results are as shown in the last column. It can be seen that the numerical values are all in the vicinity of 7 electrons per atom. This is true also for the ternary Cr-Mo-Ni IT phase, which occurs in a system in which none of the binary compositions are known to develop the phase. In the Fe-Mo binary, the high temperature a phase, which occurs at a composition of 50 atomic pct of each element, also yields a ,;1 e of 7 electrons per atom. From inspection of Tables I and 11, it develops that any series of sequential numbers which is assigned to the elements under consideration will result in the numbers pertaining to a compositions grouping themselves around one specific number. It does not follow, however, that this random number necessarily has physical significance. Such a point has already been discussed by Hume-Rothery." One interesting point develops from this study, however, and that is the position of manganese with reference to the other elements and to the phase. In the system used here, the formation of phase is associated approximately with the value of 7 electrons per atom, which is also the number of electrons per atom that manganese has. Manganese, it will be recalled, exists in three different crystal forms, none of which are the usual, simpler metallic forms; on the other hand, elements just to the left of manganese (in Table I) generally have lower coordination-number structures (body-centered cubic) than do elements to the right of manganese (face-centered cubic). The contribution to a complex crystal structure by the interalloying of elements from opposite sides of manganese is significant in that the a phase is formed in binary systems including one element from each side of manganese, with manganese capable of participating with both sides. It is indeed an interesting coincidence that manganese, with 7 electrons per atom, solidifies in complex crystal forms, and that when alloys of the transition elements are made which have seven 3d-4s electrons per atom, they, too, tend to assume a complex crystal form. From the above, it might be deduced that the study of the a phase might be advanced by a critical examination of the element manganese and how its structure is affected by small additions of elements which change the 3d-4s electrons per atom number. The role of atom size would also be of interest in formation. References ' A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, Part 4, p. 173. 2 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951). "W. Hume-Rothery, H. M. Irving, and R. J. P. Williams: The Valencies of the Transition Elements in the Metallic State. Proc. Royal Soc. (September 1951) 208A. p. 431.

Jan 1, 1954

By R. H. McLean

Jet impingement produces two mechanisms to clean the bottom of a borehole during jet-bit drilling operations. One is an impact-pressure wave in the immediate area of jet impingement. The other is crossflow, which spreads across the bottom away from the pressure wave. Measurements of the vertical distribution of the cross-flow at several positions beneath a 4 3/4-in. tricone jet bit in a laboratory model show that the maximum velocity in the crossflow is directly proportional to the square root of the product of the rate of flow and the velocity of the jets through the nozzles (QV). Other measurements in the laboratory model show that gradients in the impact-pressure wave are directly proportional to the jet QV if the diameters of the nozzles are held constant. Consistency of the basic relationships through changes in the Reynolds numbers of the jets from 31,000 to 93,000 suggests that the laboratory results should be representative of typical flow in field operations having higher Reynolds numbers. Estimates of the impact-pressure waves under conditions other than those in the jet-bit model may be made by comparison with a less complex model—impingement of a jet against an unrestricted flat surface normal to the jet. Equations derived from current jet technology describe the wave in this simple system for a wide range of conditions. INTRODUCTION The efficiency of rotary drilling operations is strongly linked to the efficiency with which cuttings are removed. Cuttings remaining on the bottom of the borehole will impede further penetration by the bit until they are removed. Wasteful regrinding is prevented if the fluid circulated past the bit removes cuttings as rapidly as they are made. Most investigations of bottom-hole cleaning under bits have been concerned with the rate-of-penetration effects of bit type, nozzle configuration, fluid properties, pressure gradients and utilization of hydraulic horsepower. These investigations have shown that drilling muds, weighted to keep the pressure in the borehole greater than in adjacent formations and carrying material which forms a filter cake, apparently plaster cuttings against the bottom, making them difficult to remove. In addition to a demonstration of the factors causing poor cleaning, the most significant result of these previous investigations has been the increased use of jet bits accompanied by better hydraulic programs and better selection of drilling fluids. Undoubtedly, these practices have improved bottom-hole cleaning, but rates of penetration when drilling with muds are still often lower than would be expected with perfect cleaning." Although there is general agreement with the concept that increasing hydraulic energy at a jet bit often increases the rate of penetration by improving cleaning, research workers have differed as to the best criterion for evalyating hydraulics. Some lean toward maximizing the product of the rate of flow and the velocity through the nozzles (QV) others prefer to maximize the hydraulic horsepower at the bit;'"-' "till another says that neither criterion is universally suitable."' This controversy shows that conclusive field evidence has not established the superiority of either of these criteria. Analysis of the fluid flow which cleans the bottom should contribute to resolving the controversy. Impinging jets clean the bottom by creating two mechanisms capable of dislodging cuttings. One is the impact from the momentum of the jet and the other is the flaw parallel to the bottom away from the area of impingement. The impact force appears in the form of a pressure wave on the bottom and, in this paper, is called the impact-pressure wave. The flow parallel to the bottom is called crossflow. Fig. 1 illustrates these two mechanisms. This paper describes crossflow and the impact-pressure wave beneath jet bits and relates them to controllable parameters. Through these relations, criteria for use in designing hydraulics to achieve maximum use of the mechanisms of cleaning are derived. PROPERTIES OF CROSSFLOW CONCEPTS DEVELOPED IN PREVIOUS INVESTIGATIONS Concepts of scavenging the bottom by crossflow have been well discussed by Bobo, et al." They examine the means by which crossflow may create forces on cuttings and conclude that the cleaning action of crossflow can be increased by increasing the velocity of the flow stream close to the bottom. Using boundary layer theory, they indicate that a reduction in the viscosity of the drilling

Jan 1, 1965

By V. F. Hollister

The Queen Charlotte gold deposit (also known as the Specogna, Babe, or Cinola) was discovered in late 1970 by Efrem Specogna and Johnny Trico. They were prospecting along the trace of the Sandspit fault, and they sampled jarositic material that included veins from the fault zone. Their assays included some good gold values. They located the Babe Claims in 1971 and optioned them to Kennco Explorations Ltd. Kennco conducted stream sediment and soil geochem studies, geological mapping and drilling of 55.2 m (181 ft) in two drill holes. Kennco withdrew from the property, and by 1977, Cominco, Placer Development, Silver Standard, and Quintana Minerals had each successively worked on the deposit. Consolidated Cinola Mines bought the claims in 1977 and completed exploration of the deposit ultimately in a joint venture arrangement with Energy Reserves. Energy Reserves entered in late 1979, and by 1983, a total of 200 surface and 12 underground drill holes had been completed, totaling 28 600 m (93,832 ft). In addition, a 461.9 m (1515 ft) adit was driven in the ore body. Reserves published by Cinola aggregate 34 Mt (37 million st) of 1.7 g (0.060 oz) Au per tonne. All industry geologists working in the area agree that the Queen Charlotte gold is an epithermal gold deposit in porous volcaniclastic and clastic rocks that is genetically related to a Miocene-Pliocene rhyolite plug. The geologic description here follows the oral presentation made by G. G. Richards, J. S. Christie, and M. R. Wolfhard at a 1976 CIM meeting. Additional comments by the late C. S. Ney of Kennco Explorations are included with the Richards, Christie, and Wolfhard data to complete the geologic set- ting. The attached reprint by Champigny and Sinclair (1 980) provides additional data on the deposit. The Queen Charlotte (Babe, Specogna, or Cinola) gold deposit is located on Graham Island in the northern Charlotte Islands, at the fault boundary of the Skidegate plateau and the Charlotte lowlands. The Sandspit fault marks the physiographic boundary, and it is intruded by rhyolite porphyry at the deposit. Because displaced geochem anomalies, drain- age patterns, and topography suggest dextral and east side down movement for the fault, exposed east block rocks are younger than rocks west of the fault. The east block, which included the ore deposit, is a lowland largely masked by unconsolidated Pleistocene and Recent clastic rocks. Rocks west of the rhyolite plug, on the Skidegate plateau, are Cretaceous carbonaceous and calcareous shale unconformably overlain by a thin veneer of rhyolite tuff. The deposit is about 100 m (328 ft) above sea level. GEOLOGIC SETTING At the ore deposit, the Sandspit fault is a complex structure. However, lithologies on either side of the fault-controlled rhyolite porphyry plug are distinct. West of the rhyolite, the upper member of the Cretaceous Haida formation shale is the most common rock type. The member is composed of dark grey to black, poorly consolidated, and thinly bedded carbonaceous and calcareous shale. The sequence is silicified to an argillite or a hornfels near the rhyolite. West of the rhyolite porphyry plug, but not importantly involved in the mineralization, is a thin masking cover of rhyolite tuff. The tuff unconformably succeeds the cretaceous shale, but it is largely eroded in the mine area. East of the fault-controlled rhyolite porphyry plug is a thick section of conglomerate and sandstone of the Miocene- Pliocene Skonun formation. The ore body occurs within the coarse clastics, the rhyolite intrusive as the western boundary. Ore is entirely contained within the clastics. Original permeability of the clastic rocks was a major control for ore deposition and alteration, and for that reason, the Skonun formation is described in greater detail. The Skonun formation clastics unconformably overlie Haida shale. The Skonun is at least 300 m (984 ft) thick in the mine area, where it trends northerly and dips easterly 15º to 25º. The sequence is about 62 percent conglomerate, 3 1 percent coarse arkosic sandstone, and 7 percent interbedded siltstone and sandstone. Contacts between adjacent beds are generally sharp. Stratigraphic correlations between drill

Jan 1, 1985

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By H. Groeneveld, C. A. Connally, P. J. Hoenmans, J. J. Justen, W. L. Mason

A miscible displacement pilot using a slug of LPG driven by separator gas was conducted in the Cardiurn reservoir of the Pembina field. The injection pattern was a 10-acre, inverted, isolated five-spot. Upon completion of the LPG-gar phase, an experiment was conducted using a slug of water followed by gas. Calculated performance of the pilot is compared with actual performance. Equations are developed to calculate the distribution of LPG into zones of varying permeability, to estimate the progress of the flood at different times in the various zones and to estimate gas rates after breakthrough. The analysis indicates that permeability stratification was a dominant factor in controlling oil recovery and that oil was completely displaced from the swept pore volume. The results of the pilot indicated that miscible flooding is a practical means of pressure maintenance in this reservoir. The total recovery from the pilot area was good in spite of the early breakthrough of LPG. The effects of stratification were reduced by injecting a slug of water into the partially swept reservoir. INTRODUCTION The Pembina field,' located in Alberta, is the largest oil field in Canada and one of the largest in the North American continent. The reservoir is a stratigraphic trap producing from the Cardium sand. Neither bottom water nor free gas has been found. The recovery of oil by the natural depletion mechanism has been estimated at 12.5 per cent. Pressure maintenance studies of various areas have indicated that the recovery can be increased 21/2 times by water flooding, and a large area of the field is presently under water flood. However, reservoir studies of the North Pembina area indicated that miscible flooding might be competitive with water flooding. A pilot test was conducted to evaluate the performance of a miscible flood. A 10-acre, inverted, isolated, five-spot pattern was selected for the pilot. The pattern area was large enough to minimize wellbore fracturing effects and contained sufficient oil to provide significant working numbers. The performance of each of the four producers could be evaluated individually and compared. In the event of breakthrough in one direction, the effect would be isolated from the other producers. The use of a single injector minimized the volume of LPG required, and, because of the high mobility of gas, one well was sufficient to inject the necessary daily volume to replace the high rate of production. With four producers, the test could be completed in time for results to be evaluated, additional engineering studies to be made and a unit to be formed before the reservoir pressure in the North Pembina area declined below the bubble point. The pilot was located in an area developed on staggered, 80-acre spacing. The injection well was drilled at a regular location, while the four producers were drilled 467-ft north, east, south and west of the injector. Each quadrant and its associated producer were identified according to their direction from the injector— that is, north, east, south or west. The eight surrounding producers on 80-acre spacing were shut in to isolate the pilot area and provide for reservoir pressure observation. The pilot wells were completed using permanent-type completion techniques. After coring, casing was run through the pay section and cemented. Inside 51/2-in. casing, 2 1/2-in. tubing was hung. The wells were perforated opposite the Upper Cardium sand and lightly fractured. Fracturing volumes, rates and pressures were low to minimize the extent of the fractures. The fracturing treatments average 1,000 lb of 20-40 mesh sand in 700 gal of a low fluid-loss sand-carrying agent. Feed rates and wellhead fracturing pressures averaged 5.5 bbl/min at 2,535 psig, respectively. After fracturing, the productivity index was measured in each of the five pilot wells. The average PI of the four producers was 0.41 BOPD/psig drawdown. The measured PI'S were approximately the same as PI'S calculated from core analysis data, indicating that the fracturing treatments were just sufficient to overcome

By Robert W. Hunt

(Cleveland meeting, October, 1912.) PERHAPS of all the scientific economic questions which have been claiming the attention of capitalists, metallurgists, manu-facturers, directors of public utilities, and the general public of America, during the last few years, none have been of more importance than the one relating to the wear and safety of steel rails. The discovery of the Bessemer process made possible modern railway development. In that growth, as has generally happened in all progressive movements, ill its department have not remained equally balanced. Iron rails permitted the construction of roadways for the passage of power-driven vehicles. In time the speed and weight of such carriages proved too much for the wearing-qualities of the rails, and the limit of railway capacity seemed to have been reached. Bessemer made his invention, which was soon perfected and developed, especially as related to steel rails, and thereby increased the limit of capacity, acid vastly greater railway progress was, made possible. The Siemens-Martin open-hearth process followed, and was later supplemented by the Thomas-Gilchrist basic improvement. For a time the Bessemer steel rails of commerce Were, more than equal to all that was asked of them, but this did not long continue, as evidenced by the records in our Transactions. Revolutionary changes occurred in the industrial world, and in no part of it more than in steel-rail manufacture. Great and powerful commercial combinations were made, whose financial resources made possible the supplanting of the then most efficient blast-furnaces, steel-works, mid mills, by others of theretofore unimagined capacity. Old traditions and practices of steel-making were wiped away, and, in too many cases, output was apparently the chief aim, with the result that much dissatisfaction with the wear and safety of rails was felt by railway officials, and the general public was concerned as to its safety when traveling. The climatic conditions of the winter

Dec 1, 1912

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By M. D. Hassiallis

The claim is made in a number of patents1'2'3'4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S2-R' (where x = 1,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using diphenyl sulphide, ditolyl disulphide and dinapthyl disul-phide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed. was that of Moses, Hess, and Perkins. A sample of ore weighing 500 • grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65-mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a a-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8:I. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of I2:I. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. Contact-angle Tests In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcodte, chalco-pyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By Willard R. Jillson

Within the last ten years Kentucky has become celebrated for its low-sulfur bituminous coals. Prior to this time, many investigators had discnvered the abundance of this coal but the fact was unknown to the general public until the last extension of Kentucky's mountain railroads' was completed. The coals of. Kentucky are, broadly, separated into two geographic units—the eastern and the western coal fields. On a basis of their sulfur content these coal fields fall into three units, which are indicated on the accompanying map, by numbers, 1, 2, and 3. The area marked 1, the very southeastern part of the state, shows the lowest sulfur, all coals being averaged. In this field the maximum is 1.04 per cent. and the minimum as low as 0.68 per cent.—both averages and not individual analyses, which would of course show much greater variation. Included in this group are the following counties: Lawrence, 0.87 per cent.; Martin, 0.75 per cent.; Johnson, 0.73 per cent.; Magoffin, 0.87 per cent.; Floyd, 0.88 per cent.; Pike, 0.68 per cent.; Knott, 1.04 per cent.; Perry, 0.77 per cent.; Letcher, 0.80 per cent.; Leslie, 0.70 per cent.; Harlan, 0.79 per cent.; Knox, 0.86 per cent.; and Bell, 0.92 per cent. The total average sulfur content for these thirteen counties is 0.82 per cent. Bordering the restricted low-sulfur field of eastern Kentucky is the No. 2 belt (slightly darker), 'which is commonly known as the western border of the eastern coal field. Here the maximum sulfur is 2.91 per cent. and the minimum 1.05 per cent. Again these are averages and not individual analyses. The counties in this group are: Greenup, 2.60 per • cent.; Boyd, 1.67 per cent.; Carter, 1.07 per cent.; Morgan, 1.40 per cent.; Wolfe, 1.83 per cent.; Lee, 2.93 per cent.; Breathitt, 1.85 per cent.; Owsley, 1.09 per cent.; Jackson, 1.06 per cent.; Rockcastle, 2.30 per cent.; Clay, 1.09 per cent.; Laurel, 1.08 per cent.; Pulaski, 2.24 per cent.; Whitley, 1.05 per cent.; McCreary, 1.50 per cent.; and Wayne. The sulfur percentage average for this area including fifteen important counties is 1.65 per cent. In the western Kentucky field, the great increase in the percentage of sulfur is at once apparent. Ohio County with 3.78 per cent. is the highest and Hancock with 2.87 per cent. is the lowest. The percentages by counties is as follows: Hancock, 2.87 per cent.; Henderson, 3.22 per cent.; McLean, 3.27 per cent.; Muhlenberg, 3.31 per cent.; Hopkins,

Jan 1, 1920

By M. D. Hassialis

THE claim is made in a number of patents1,2,3,4 that some compounds of the class known as aryl sulphides have collector properties. One of these patents generalizes the claim to include all aryl sulphides, whose generic formula is R-S¬R[=]-R’ (where x = r,2, . . . ), with the restriction that if the aromatic radicals R, R' contain substituent groups these groups may not contain nitrogen or oxygen. Moses, Hess, and Perkins cite as evidence for their claims the results of flotation tests on Anaconda and Miami copper ores using Biphenyl sulphide, ditolyl disulphide and dinapthyl disulphide as collectors. The use of alkyl sulphides as collectors has also been reported5 with the conclusion that the alkyl sulphides are better collectors than the corresponding aryl sulphides. The experimental work cited appears to confirm this contention. In order to test these claims with respect to diphenyl sulphide, a sample, purchased from the Eastman Kodak Co., was tested against Anaconda ore. The procedure followed was that of Moses, Hess, and Perkins. A sample of ore weighing 500 grams was placed in a laboratory ball mill. To this was added 220 grams of water, 0.06 grams of commercial diphenyl sulphide (1/4 lb. per ton of ore), and 0.8 grams of lime (3 lb. per ton of ore). The material was ground until 93 per cent passed a 65mesh screen. This pulp was diluted to 16 per cent solids. A sample of the diluted pulp was placed in a Minerals Separation type of laboratory flotation cell. After a 2-min. agitation period, pine oil was added and the froth collected for a period of 15 min. This test recovered 68 per cent of the copper, with a ratio of concentration of 6.8: 1. The tailing assay was 0.3 per cent Cu. Moses, Hess and Perkins attained a recovery of 75 per cent, with a ratio concentration of 12: 1. Although these results do not compare too well with those of Moses, Hess and Perkins, subsequent tests showed an improvement, as judged by vanning of the tails. It is concluded, therefore, that the patent results are confirmed. CONTACT-ANGLE TESTS In order to study the response of the various minerals, found in Anaconda ore, to commercial diphenyl sulphide, some contact-angle tests were made. Polished particles of bornite, chalcocite, chalcopyrite, pyrite and quartz were conditioned for 15 min. in a suspension of diphenyl sulphide in water. The concentration of this suspension was 0.284 grams per liter, this being the concentration of this reagent in the ball mill. The conditioned particles were rinsed with water (not rubbed with filter paper or boiled linen) and then tested against an air bubble in the bubble machine, with the following results: born-

Jan 1, 1943

By A. W. Fahrenwald

CELL depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence-i.e., the depth in the pulp at which the impeller is required to produce aeration. THE FLOTATION MACHINE A COMPRESSOR A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure[t] (14.7 lb. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 lb. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 lb. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 [-] 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 [=] 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the finer, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. THE FLOTATION MACHINE AS A PUMP Since, in impeller machines that rely upon their own operation to produce aeration, pulp passes through the im-

Jan 1, 1946

By W. T. Bishop

For many years pine oil has been used extensively as a frother for the flotation of minerals, particularly sulphides, yet the published information available to the average user on its composition, chemical and physical properties, has been rather meager. It is the purpose of this paper to discuss these points and their relationship to the frothing properties of pine oil used in flotation processes. Pine oil, as the name implies, is a liquid obtained from the processing of wood of the longleaf and other southern pines. It is a complex mixture of naturally occurring terpene derivatives, primarily alcohols, and a smaller amount of terpenes, which has found many uses in various industries. Its use as a frother in flotation processes was the first large-scale application in industry and today the mining industry still consumes large quantities of pine oil but the textile and disinfectant industries consume comparable volumes. Much is used in soap manufacture and laundry operations. The surface-active properties of pine oil are in a large degree responsible for this versatility. History The name "Naval Stores" goes back to the days when pine tar and pitch were used to caulk leaky ships and 'Oat their ropes and rigging. Today this term is still used to include not only the oleoresinous products of the pine tree—rosin and turpentine— but other products such as pine oil, pine tar, and the many terpene and resinous compounds obtained by extracting the pine wood or tapping the tree. That part of the industry known as "wood naval stores" dates from about the beginning of this century and today produces a large part of the country's rosin and turpentine by processing pine wood. In addition, all of our natural pine oil is supplied by the wood naval stores industry, as tapping of the live tree gives only rosin and turpentine. This latter phase is known as the "gum naval stores " industry. The first successful commercial operation of the steam and solvent process of the wood naval stores in industry was carried out by Yaryan at Cadillac, Mich., in 1909.1 This operation did not prove profitable, so Yaryan went south to utilize the longleaf pine, and built a plant at Gulfport, Miss.2 Soon after, another plant was built at Brunswick, Ga., which is still in operation, and in 1914 was reported to have processed about 500 tons of wood per day.' In 1921 Hercules Powder Co. acquired the Yaryan interests, at which time the production of pine oil was only 3 to 5 million pounds per year and flotation was the largest customer. As time went on, technological advances were made, other companies entered the field, and the production of pine oil increased many fold. The growth of the industry was especially marked during the past 10 years, and in

Jan 1, 1947