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By Persifor Frazer

The rocks which cover the east flank of the South Mountain are chloritic schists typical in character. A specimen of this rock from near the Bechtel shaft, Hamilton Ban Township, Adams County, Pa., was selected and analyzed in my laboratory by Mr. C. Hanford Henderson, with the following results: Ignition,........2.740 CaO,..........7.040 SiO,,..........41.280 MgO,.......... 7.486 AI,O,,.........18.480 K,O,..........2.208 Fe,Os,.........9.440 Na,O,.........3.523 FeO,......... 8.200 100. As one penetrates the range by moving westvard, these schists are replaced either by epidotie quartz or by orthofelsite. In the former case, a belt of copper-bearing rock is traversed, but not in the latter case. Inasmuch as this junction of the chloritic schists on the southeast and orthofelsite on the northwest, separated by the epidotic quartz, is several times repeated, we find two or three copper belts arranged in general parallelism to the axis of the chain, because the copper horizon is generally at this junction. Thus, in going west from Fairfield, after entering the low spurs on the South Mountain, one is fairly within the chlorite measures. At the " Virginia Mills " a chlorite schist comes in with a dip of S. 1.5 E.-74 Half a mile up Middle Creek, large numbers of fragments of chlorite schist, decoruposed epidotic matter, and quartz are encountered. The former rock, where in place, dips E. 40" S.-57o. About 4000 feet west of the intersection of this road with the so-called Tape-Worm Railroad, near the house of one Singly, large masses of chloritie schist are found loose on the road. A hundred yards farther west, near a triangle in the road, the latter is less in quantity and much epidotic quartz appears, after which a very large display of orthofelsite succeeds on the left bank of Middle Creek. All these last-mentioned rocks, however, are in fragments. Crossing the stream again a few hundred yards farther On, the chlorite fragments at first preponderate, and then large numbers of both rocks

Jan 1, 1884

By Daniel M. MacNeil, Carle R. Hayward, Raymond L. Presbrey

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By Daniel M. MacNeil, Raymond L. Presbrey, Carle R. Hayward

At the February, 1916, meeting of the Institute, a paper presented by Hayward and Raymond gave the results of a study on the effect of time in tempering medium-carbon steel, when the following conclusions were reached: It is not fair to consider the question settled when only three specimens were used for each treatment, but the results obtained indicate that for reheating quenched medium-carbon steel to temperatures below 500" it is only necessary to heat it through. Longer heating has little or no effect on the tensile strength, ductility, or hardness. At temperatures above 500°, increasing the time of treatment causes a slight falling off in hardness and tensile strength with a corresponding increase in ductility. In the discussion of the paper these conclusions were attacked and evidence was presented that seemed to throw doubt on their accuracy. The authors, however, showed that this evidence was based on high-carbon or alloy steels and no facts regarding medium-carbon steel were presented. During this study the heat treatment was carried out in a small electric resistance furnace. It held nine specimens, but when these were placed in the furnace the temperature was lowered to such an extent that 30 to 40 min. were required to reach the desired heat. The authors pointed to this as a weak point in the investigation and it seemed wise to supplement the research by work on similar steel but using a different method of heating. This has been done and the results are given in the present paper. The Rhode Island Tool Co. coöperated by furnishing the steel and turning the tensile specimens. The steel used in this investigation came in three bars 3/4 in. in diameter; analyses are as follows: Carbon. MaNGanese, Phosphorus, Sulfur Bar NUmber PeR Cent. Per Cent. Per Cent. Per Cent. 1 0.46 0.56 0.010 0.055 2 0.44 0.58 0.007 0.042 3 0.48 0.58 0.007 0.048

Jan 1, 1922

By F. Forscher

Pronounced porosity, decreasing with distance from the fracture surface, is found in the necked region of tensile specimens tested at room temperature or liquid nitrogen temperature. A hydrogen solution treatment followed by a quench prevents pore formation in tests at —196°C, but has little effect on tests made at room temperature. Reduction of area values at —196°C are strikingly improved by the same treatment, but show no improvement in room temperature tests. The experimental results support the hypothesis that strain-induced porosity results with hydride initially present or, in material containing less than 50 ppm H, with hydride precipitated by strain aging. ZIRCONIUM'S advent as an engineering material in nuclear reactor construction has brought forth many investigations concerned with the properties of this metal and its alloys. Some attention has been given to the ductility of the metal.1, 2 Particularly, the effect of hydrogen on the impact strength was noted," indicating a pronounced dependence of ductility on the hydrogen content and its distribution in the metal. Micro graphic:' and X-ray diffraction studies' have shown that a precipitated hydride phase causes embrittlement in zirconium,' which implies a distinctly different mechanism from that causing hydrogen embrittlement in steels."-' In the latter case, it is assumed that atomic hydrogen diffuses to rifts, where it forms molecular hydrogen under such internal pressures that it causes the rifts to enlarge, leading to fracture. Thermo-dynamic studies of the Zr-H system8, 9 also indicate that the internal pressure of molecular hydrogen would be too low to cause any damage to the zirconium at room temperature, and the formation of a zirconium hydride (d phase) is favored." It is noteworthy that this phase has a face-centered-cubic structure and nearly 18 pet larger molar volume than close-packed-hexagonal a-zlrconlum' Other features of the ductility of zirconium are the absence of a typical cup-cone failure upon tensile testing, a pronounced strain-induced porosity in the necked region of a tensile bar, Fig 1, and the associated spongy appearance of the fracture surface A tremendous improvement in ductility at liquid nitrogen temperature can be observed following a heat treatment that retains the commonly present quan- tities (10 to 50 ppm) of hydrogen in solution. Such tests show a typical cup-cone failure and the absence of strain-induced porosity, Fig. 2. The present paper reports results of an investigation into the causes of strain-induced porosity in zirconium. Room temperature tensile fractures of mild steel, aluminum, and titanium have also been examined for strain-induced porosity. In each case porosity could be detected, but the amount was orders of magnitude less than was found in zirconium. Of the three metals, titanium showed the strongest effect. Material, Specimens, and Preparation The greater part of this investigation was done on Westinghouse crystal bar zirconium, are-melted, forged, and hot-rolled. Chemical analyses of the hot-rolled plates are given in Table I, along with those of the Foote crystal bar zirconium used in this work. The specimens were machined from the hot-rolled plate (1550°F) of 1/2 in. thickness and subsequently heat-treated according to one of the treatments shown in Table IS. All specimens were machined round, the longitudinal axis in the rolling direction, with a gage

Jan 1, 1957

By A. Lubinski

In drilling operations, attention generally is given to hole angles rather than to changes of angle, in spite of the fact that the latter are responsible for drilling and production troubles. The paper presents means for specifying maximum permissible changes of hole angle to insure a trouble-free hole, using a minimum amount of surveys. It is expected that the paper will result in a decrease of drilling costs, not only by avoiding troubles, but also by removing the fear of such troubles. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS Excessive dog-legs result in such troubles as fatigue failures of drill pipe, fatigue failures of drill-collar connections, worn tool joints and drill pipe, key seats, grooved casing, etc. Most of these detrimental effects greatly increase with the amount of tension to which drill pipe is subjected in the dog-leg. Therefore, the closer a dog-leg is to the total anticipated depth, the greater becomes its acceptable severity. Very large collar-to-hole clearances will cause fatigue of drill-collar connections and shorten their life, even in very mild dog-legs. Another finding regarding fatiguing of collar connections in dog-legs is that rotating with the bit off bottom sometimes may be worse than drilling with the full weight of drill collars on the bit, mainly in highly inclined holes when the inclination decreases with depth in the dog-leg. Means are given for specifying maximum dog-legs compatible with trouble-free holes. An inexpensive technique proposed is to take inclinometer or directional surveys far apart; then, if an excessive dog-leg is detected in some interval, intermediate close-spaced surveys are run in this interval. The application of the findings should result in a decrease of drilling costs, not only by avoiding troubles, but mainly by removing the fear of such troubles. The result would be much more frequent drilling with heavy weights on bit, regardless of hole deviation. Because of errors inherent to their use, presently available surveys are not very suitable for detecting dog-legs. There is a need for instruments especially adapted to dog-leg surveys. Crooked hole drilling rules should fall into two distinct categories—(1) those whose purpose is to bottom the hole as desired, and (2) those whose purpose is to insure a trouble-free hole. Three kinds of first-category rules in usage today are as follows. 1. A means to bottom the hole as desired is to prevent the bottom of the hole from being horizontally too far from the surface location; this may be achieved by keeping the hole inclination below some maximum permissible value such as, for instance, 5. 2. Another means to achieve the same goal is to limit the rate at which the inclination is allowed to increase with depth. A frequently used rate is 1/1,000 ft. In other words, a maximum deviation of l° is allowed at 1,000 ft, 2 at 2,000 ft, 3 at 3,000 ft, etc. 3. Whenever application of the first two means precludes carrying the full weight on bit required for most economical drilling, then the best course is to take advantage of the natural tendency of the hole to drift updip, displace the surface location accordingly and impose a target area within which the hole should be bottomed. This method has already been successfully applied,'.' and its usage probably will become more frequent in the future. Means for calculating the amount of necessary surface location displacement are avail-able.3'5'6 If in high-dip formations the full weight on bit should result in unreasonably great deviations, the situation could be remedied by increasing the size of collars and (if needed) the size of both hole and collars,351 or in some cases by using several stabilizers. Rules which would fall into the second category (i.e., rules whose purpose is to insure a trouble-free hole) are seldom specified today. It is vaguely believed that following Rules 1 and 2 of the first category will automatically prevent troubles. Actually, this is not true. If at some depth the only specified rule is that the hole inclination must be less than 4", the hole may be lost if the deviation suddenly drops from 4 to 2, or if the direction of the drift changes, etc. Rule 3 of the first category is generally used in conjunction with a rule belonging to the second category, namely, that the hole curvature' (dog-leg severity) must not exceed the arbitrarily chosen value of 1½ /100 ft. Moreover, when using this rule, the industry is not clear over what depth intervals the hole curvature should be measured. All this results in a frequent fear

By Bauer. Larry G.

The vast coal reserves in the Wyoming, Montana, North and South Dakota region are sufficient to supply the total energy needs of the United States for several hundred years. Not only is there an abundance of this sub-bituminous and lignite coal available, but it is easily obtainable by strip-mining . The overburden varies from several feet to several hundred feet. This western coal has yet another asset, namely, a low sulfur content. Whereas eastern and midwestern coal has a sulfur content of 2.5%, the upper Great Plains coal contains sulfur in the 0.5% range. The importance of the sulfur content of the coal is a direct result of federal government emission standards for sulfur dioxide (SO2). Hand (1) points out that "sub-bituminous coals and lignites have a propensity for retaining this sulfur in the ash under certain conditions which is not evident in higher rank coals." This would tend to reduce further the SO2 concentration in the combustion gases of boilers. Western coal is no panacea, however, in that it is far removed from most population and industrial centers. Furthermore, the moisture content of the coal varies from 20 to 40%. This moisture is almost exclusively inherent, that is, it is chemically and physically bound to the organic matter of the coal. It is believed that the water forms a part of the coal structure perhaps as water of hydration of organic salts or organic acids, perhaps by hydrogen bonding, or perhaps by simple adsorption (2). The primary market for this coal is the electric power industry. Lesser markets will be as coke for the steel industry and possible as a raw material for coal gasification and coal liquefaction plants.

Jan 1, 1983

By H. C. Theuerer

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

Jan 1, 1957

By H. L. Luo, W. Klement

By rapidly quenching Ag-Pt alloys from the melt, a continuous series of solid solutions has been obtained. At equilibrium''2 these fcc elements form a peritectic system, Fig. 1. Weighed amounts of silver and platinum powder (325 mesh, purity greater than 99.9 pct) were mixed for 24 to 120 hr, pressed into compacts, sintered at 1000°C in a hydrogen atmosphere for at least 16 hr, and then furnace-cooled. Because of the difficulty in achieving homogeneity in alloys containing more than about 40 at. pct Pt, the sintered compacts were induction-melted under hydrogen in alumina crucibles and then cold-rolled into wires. Small amounts ("30 mg) of alloys cut from various sections of the sintered compacts or rolled wires were heated to at least 50' ~ above the liquidus in an alumina insert held within an induction-heated graphite crucible; then the molten alloy was ejected by a blast of helium onto a lightly polished copper strip held on the inner periphery of a rotating wheel. The flakes thus obtained were typically 1 sq mm in area or often slightly larger for the silver-rich alloys. X-ray diffraction patterns were obtained with nickel-filtered copper K radiation in a 114.6-mm-diam Debye-Scherrer camera with rotated specimens. Lattice parameters and associated uncertainties were estimated from extrapolations against the Nelson-Riley function. High-angle lines were always resolved and spacings were computed relative to r(CuKa!,) = 1.540508 The details of these techniques have been discussed previously.s'6 Lattice parameters of the solid solutions are plotted in Fig. 2, together with the data of Schneider and Esch,' Johansson and Linde,' and Novikova and pudnitskii. Each of the present lattice spacings represents two or more independent determinations. The alloys were homogeneous within 2 at. pct of nominal composition as estimated from the uncertainties in the lattice spacings. Many of the mechanisms involved in the achievement of metastable solid solutions by rapidly quenching from the melt have been previously discussed. There is some evidence" that such solid solubility cannot be obtained when the liquid alloys are cooled

Jan 1, 1963

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.' The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.' and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,' or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969

By Alfred Siegel

Mineral pigments give color, opacity, or body to paint, stucco, plaster, mortar, cement, linoleum, rubber, and similar materials. They must be finely divided, substantially insoluble, and generally inert for such uses. Inorganic pigments may be grouped somewhat arbitrarily as follows: A. Natural mineral pigments dug from the earth. 1. Those consisting mostly of iron oxides, such as hematite and limonite. 2. Those containing large amounts of clay or noncoloring matter, such as ocher, sienna, umber, and colored shales. 3. Those whose color is not due to iron oxide, such as Vandyke brown (including sap brown, an alkali extract of Vandyke brown), graphite, and terre verte. B. Synthetic pigments. 1. Those containing iron oxide as the essential coloring matter, such as "pure" reds, yellows, and blacks, and Venetian reds. 2. Those not containing iron oxide, but rather such compounds as lithopone, zinc white, titanium white, ultramarine, Prussian blue, and the like. Only groups A and B-1 are discussed here. All the pigments in those two categories, except Vandyke brown, sap brown, and some of the carbonaceous slates, contain, as their essential color constituents, one or more compounds of iron; namely, an oxide-limonite (2Fe2O3.H2O to Fe2O3.4H20), hematite (Fe2O3), or magnetite (Fe2O3.FeO). Man's first permanent coloring materials were earth pigments-the ochers, iron oxides, and various iron-stained clays. The caves occupied by prehistoric man and the arts of the ancient Chaldean, Egyptian, and Cretan civilizations bear mute witness to this and also testify to the beauty and permanence of earth colors. As the Roman era developed, earth pigments were pushed from their pre-eminent position by white lead and red lead and in the Middle Ages by zinc oxide. Today, of course, the number of acceptable pigments is very large and on a value basis the group of natural and synthetic earth pigments stands forth with $16,000,000 per year; it is surpassed by titanium, lead and zinc pigments. Of this sum,21 natural pigments supplied 31 pct of the tonnage and 16 pct of the value of the total finished pigment in 1957, the remainder representing the tonnage and value of sales of the synthetic iron oxide colors. The average value of finished natural pigments in 1958 was $80.62 per ton. The average value of manufactured pigments in the same year was $202 per ton. Of the 60,000 tons of manufactured colored pigments sold in 1958, the reds comprised 76 pct of the market and the yellows 20 pct. The reds furnished 68 pct of the value and the yellows 24 pct. Of the finished iron oxide pigments (natural and manufactured) sold in 1958, the reds dominated the market with 66 pct of the quantity and 63 pct of the value; yellows supplied 17 pct of the quantity and 20 pct of the value, and browns furnished 11 pct of the quantity and 10 pct of the value. The average value of the reds was approximately $152, and the average value of the yellows $190 per ton. The highest valued pigment in 1958, with almost 12 pct of the total tonnage and 21 pct of the value of the iron oxide pigment market, was manufactured red from calcined copperas valued at $286 per ton.

Jan 1, 1960

By Robert Mehl

THE precipitation of the nitride Fe4N from the solid solution of nitrogen in a Fe and of the phosphide Fe3P from the solid solution of phosphorus in a Fe both lead to the formation of structures that may be easily identified as Widmanstätten figures, within the meaning of the term as used in this series of papers. A complete solution has been obtained for the figure formed by Fe4N. The structure of Fe,P, however, is not fully known and a complete solution of this figure thus cannot be obtained; nevertheless, a study of this figure has furnished some new information. PRECIPITATION OF FE4N FROM ALPHA SOLID SOLUTION OF N IN ALPHA FE Constitution of System Iron-nitrogen A knowledge of the constitution of the whole of the Fe-N system is unnecessary for this work, though the recent studies by Eisenhut and Kaupp1 and by Lehrer2 have clarified most of the moot points; it is sufficient for our purpose to state that a Fe of high purity dissolves 0.42 per cent of nitrogen in solid solution at the eutectoid temperature, 591° C., and that this solubility decreases at first rapidly and then more slowly until at room temperature the solid solubility amounts to approximately 0.1 per cent nitrogen.3

Jan 1, 1934

By T. R. Lippard

PURE gypsum may be broken down into its constituents as follows: [ ] Standard specifications (ASTM Designation C22-25) state that a material shall not be considered gypsum if it contains less than 64.5 pct by weight of CaS042H2O. Anhydrite, the second calcium sulphate mineral found in nature, may be broken into its constituents as follows: [ ] PROPERTIES OF GYPSUM AND ANHYDRITE Pure gypsum is colorless to white but various impurities change its color to shades of gray, brown, red, or pink. It has a hardness of 2 in the Mohs scale and can be scratched with the fingernail. The specific gravity of pure gypsum is 2.3 to 2.4, so that rock gypsum, free from moisture, weighs about 145 lb per cu ft. Gypsum crystallizes in the monoclinic system in tabular crystals that exhibit good cleavage

Jan 1, 1949

By Tedsen L. F., Dorn J. E., A. E. Flanigan

since aluminum-alloy sheet may be used occasionally at moderately elevated ternperatures, the effects of temperature on the mechanical properties are of interest. Recently the short-time tensile properties of several high-strength materials have been studied at temperatures up to 3750°F.l This paper deals with stress-rupture and creep properties at the same temperatures. The work was done at the University of California as a portion of the project NRC-548. It was financed by the War Production Board and was supervised by the Office of Production Research and Development. This paper has been released for publication by the latter agency. The following materials were studied, all in the form of 0.040-in. sheet: Alclad 24s-T Alclad 24s-T8I Alclad 24s-T86 Alclad 75s-T R3oI-T (clad) Specimens were loaded in tension in the cross-grain direction. Testing temperatures included 94°F., 2II°F., 300°F., and 375°F. Stress levels were selected to cause rupture in times ranging from several minutes to 1000 hr. In each test the following data were obtained: (I) fracture time, (2) elongation at fracture, (3) the complete strain-versus-time curve (creep curve), (4) creep rate (defined in a later section). Materials Materials for specimens were obtained from the manufacturers' commercial

Jan 1, 1947

By Tedsen L. F., Dorn J. E., A. E. Flanigan

since aluminum-alloy sheet may be used occasionally at moderately elevated ternperatures, the effects of temperature on the mechanical properties are of interest. Recently the short-time tensile properties of several high-strength materials have been studied at temperatures up to 3750°F.l This paper deals with stress-rupture and creep properties at the same temperatures. The work was done at the University of California as a portion of the project NRC-548. It was financed by the War Production Board and was supervised by the Office of Production Research and Development. This paper has been released for publication by the latter agency. The following materials were studied, all in the form of 0.040-in. sheet: Alclad 24s-T Alclad 24s-T8I Alclad 24s-T86 Alclad 75s-T R3oI-T (clad) Specimens were loaded in tension in the cross-grain direction. Testing temperatures included 94°F., 2II°F., 300°F., and 375°F. Stress levels were selected to cause rupture in times ranging from several minutes to 1000 hr. In each test the following data were obtained: (I) fracture time, (2) elongation at fracture, (3) the complete strain-versus-time curve (creep curve), (4) creep rate (defined in a later section). Materials Materials for specimens were obtained from the manufacturers' commercial

Jan 1, 1947

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By George J. Bancroft

It is unnecessary to repeat here the contents of many valuable contributions to this subject which have appeared in the Dansactions and in the publications of the U. S. Geological Survey. As a basis for the further suggestions of this paper, the following are the most important: 1. The investigation of J. R. Don,' showing the gold of certain Australasian veins to have been deposited by ascending solutions, and not by lateral secretion. 2. The theory of Prof. Posepny? distinguishing the vadose from the deep circulation, and ascribing the origin of certain classes of ore-deposits to ascending solutions of the latter class. 3. The theory of Prof. Van Hise,3 as to the underground circulation and the primary enrichment of veins thereby. 4. The paper of Prof. J. F. Kemp,4 showing that ore-deposits are largely the products of " expiring vulcanism." Many. of Prof. Kemp's ideas have been widely adopted by mining men. 5. The theory of secondary enrichment, so lucidly expounded by Mr. S. F. Emmons.V his theory, dealing with the rearrangement of ore-bodies after primary mineralization, has been generally adopted, and seems to me to have been as completely proved as the nature of the case permits. There are two facts which I think should be constantly borne in mind in formulating a theory of the genesis of ore-

Jan 1, 1908

By W. J. Heck

The need for a better understanding of the effect of fluid pressure on the strength of intact and jointed rock has long been recognized. The behavior of pore fluid pressure was first pointed out by Terzaghi 1 who suggested the application of the effective stress concept to rock and concrete. While the effective stress concept has been used for some time in the design of mass concrete dams, it only recently has been applied to rock. Robinson 2 and Handin et al.3 evaluated the effects of pore pressure on a variety of sedimentary rocks and demonstrated the validity of the concept. Work using pore fluids other than water has been done by Boozer, et al.4 who considered strain rate and temperature as additional variables. According to the effective stress theory, the effective stress, [a], is the difference between the total stress, [a], and the pore pressure, u, and is the controlling factor influencing frictional strength of rock, other parameters remaining constant. Assuming the Mohr-Coulomb failure criteria applies, the shear strength, T, is given by the equation [r=d+ (a-u)tan ¢](1) where [~F], the angle of internal friction, and c, the cohesion intercept of "no load" shear strength, are the effective stress parameters.* Robinson,2 Handin,3 and others have demonstrated that moderately porous sand-

Jan 1, 1972

By Yap Chu-Phay

IN the previous paper, the writer showed how, on the basis of thermodynamic reasoning, it seems probable that when true equilibrium conditions obtain, carbon exists as Fe3C in the liquid state and as elementary carbon in the solid state (7 Fe), in which case the solidus would be a straight line from 0.18 to 1.70 per cent. carbon (Fig. 1). In the same paper he concluded that the solidus obtained by Honda 'and his co-workers1 probably does not represent the same conditions, insuring a complete equilibrium. Except for a downward temperature displacement, the solidus obtained by Gutowsky,2 using the Heycock and Neville method, practically coincides with Honda's solidus as shown in Fig. 1. The writer at first thought that perhaps in some way Gutowsky's thermocouple was improperly calibrated for high-temperature measurements, as his liquidus was also much lower than those obtained by Carpenter and Keeling3 and by Ruer and Goerens.4 However, the eutectic temperature obtained by Gutowsky agrees with the generally accepted value of 1130° C., so that the validity of the inference regarding improper temperature calibrations is to be strongly doubted. In Fig. 1, Gutowsky's solidus is shown both in the original and in the corrected form. In the latter, a correction of 29.2° C. is made for all temperatures above 1416° C. in accordance with-

Jan 1, 1931

By George J. Bancroft

INTRODUCTION. IT is unnecessary to repeat here the contents of many valuable contributions to this subject which have appeared in the Transactions and in the publications of the U. S. Geological Survey. As a basis for the further suggestions of this paper, the following are the most important: 1. The investigation of J. R. Don,1 showing the gold of certain Australasian veins to have been deposited by ascending solutions, and not by lateral secretion. 2. The theory of Prof. Posepny,2 distinguishing the vadose from the deep circulation, and ascribing the origin of certain classes of ore-deposits to ascending solutions of the latter class. 3. The theory of Prof. Van Hise,3 as to the underground circulation and the primary enrichment of veins thereby. 4. The paper of Prof. J. F. Kemp,4 showing that ore-deposits are largely the products of " expiring vulcanism." Many of Prof. Kemp's, ideas have been widely adopted by mining men. 5. The theory of secondary enrichment, so lucidly expounded by Mr. S. F. Emmons.5 This theory, dealing with, the rearrangement of ore-bodies after primary mineralization, has been generally adopted, and seems to me to have been as completely proved as the nature of the case permits. There are two facts which I think should be constantly borne in mind in formulating a theory of the genesis of ore-

Jan 1, 1913

By E. T. Turkdogan, L. S. Darken, R. G. Olsson, H. A. Wriedt

Several aspects of the calcination of Michigan limestone were investigated: the rate of calcination of limestone spheres with diameters from 1.8 to 14 cm at temperatures from 800° to 1200°C by a thermogravimetric method; the temperature profile across limestone during calcination; the excess pressure developed in the interior of the stone during calcination; the pore surface area, pore volume, and effective gas diffusivity in burnt lime; and the microstructure of polished and fracture surfaces. It is found that, over a wide range of experimental conditions, the difference between the surface and center temperatures remains essentially unchanged during the latter half of calcination. From the rate of weight loss after about 50% calcination, the value 0.00126 cal per cm sec degree is found for the effective thermal conductivity of burnt lime. From the excess internal pressure measurements, i.e., 0.4 to 6 cm Hg at 800° to 1200°C, the permeability of burnt lime is estimated to be within the range 8 X 10-' to 5 X 10' sq cm. With increasing temperature and time of calcination, the pore structure of burnt lime coarsens as indicated by a decrease in the pore surface area, pore volume, and an increase in the average pore size. For the temperature range 600° to 835°C the ratio (effective gas diffusivity/molecular diffusivity) is about 0.18.

Jan 1, 1974