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By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By W. L. Martin, J. N. Dew, H. B. Steves, M. L. Powers

This paper presents and discusses the results obtained during a pilot test in the Loco field in southern Okla homa. The test was conducted in a 2%-acre pattern that was part of a 20-acre conventional waterflood pilot area. The conventional flood was well past its economic limit when the hot waterflood was initiated to obtain technical information and operating experience. Temperature data from nine observation wells showed that about 75 percent of the pattern was affected by heat, and that heat losses were severe in the pilot pattern. About 60 percent of the injected heat was lost to overburden and underburden zones during hot-water injection. Wellbore heat losses were held at tolerable levels at the shallow depth of the test by providing a low-pressure air annulus between the injection tubing and well casing. Hot water provided water injectivity increases of 200 to 400 percent. The hot water channeled across the lower portion of the oil sand in three directions through zones of relatively high water saturation. There was no conclusive evidence that natural fractures or pressure partings aflected the flow of fluids in the pilot pattern; however response undoubtedly was aflected by localized pressure gradients and by injection-production rate ratios. The results showed that hot waterflooding increased oil recovery in a reservoir containing 600 cp oil. The total tertiary oil production from the pilot pattern area was 3,896 bbl or about 156 bbl/acre-ft swept by heat. The corre.sponding WOR was about 34:I. Description of the Hot Waterflood Process To hot waterflood an oil reservoir, water is injected that has been heated to a temperature substantially higher than the original reservoir temperature, but lower than the vaporization temperature of water at the prevailing pressures. In the reservoir the hot water flows continuously into cooler sand and rapidly loses heat to the sand until it has been cooled to the original reservoir temperature. Thus, a heated zone and a region or "bank" of cooled water begins to accumulate immediately after hot water injection is started. This bank of cooled water continues to grow ahead of the heated zone, which also grows, but at a slower rate. This occurs because heat transfer is almost instantaneous, and the ratio of heat capacities of water to rock is such that two or three unit PV of hot water must be injected to heat a given unit bulk volume of the reservoir. The primary displacement mechanism is the same for both hot and conventional cold waterfloods; i.e., "piston" displacement occurs at the original reservoir temperature. The incremental benefits of hot waterflooding usually occur long after the breakthrough of cold water at producing wells, and the increased oil recovery necessarily is accomplished with high WOR's (water-oil ratios). Heat decreases the viscosity and density of oil and water. These effects result in more rapid and increased recovery of secondary or tertiary oil. If the cost of the required heat is low enough, the ultimate oil recovery of a hot waterflood should be increased substantially over what would be expected at the economic limit of a conventional cold waterflood. The economic benefits of any hot-fluid injection project depend primarily upon the cost of the heat required to produce more oil at an increased rate. This cost depends in part upon the amount of heat lost to surrounding formations. Heat loss depends upon reservoir thickness, water injection rate and temperature, the depth of the formation, well spacing, and the characteristics of the reservoir rock and surrounding formations. In general, percentage heat losses decrease as injection rate and reservoir thickness increase. Although it is an old idea, hot-water injection has not received widespread field application in the oil industry as a drive process. Much of the original field work with hot water was done in Pennsylvania fields where water permeabilities and injection rates are low. In these cases, hot-water injection was used primarily as a means of increasing in-jectivities — not as a recovery process. Ramey' recently has published an excellent review of the development of hot fluid injection processes. Recent publications"' and our own experiences now indicate that hot water or steam injection also can effectively increase the oil recovery from reservoirs containing viscous crudes. However, the economics of these methods as displacement processes have not been established. Several theoretical predictive techniques have been published (for a review see Ramey'), but simplifying assumptions make

Jan 1, 1969

By H. J. Rose

In a paper1 presented before this Institute in 1926,I briefly discussed the evaluation of coking coals by means of ultimate analysis. The paper contained several graphic studies in which coal analyses calculated free of moisture, ash, sulfur and nitrogen were plotted on triaxial diagrams in which carbon + hydrogen + oxygen = 100 per cent. From a study of such data for 600 coking coals of the United States, and 150 coking coals of Wales, France and Germany, it was concluded that it was usually possible to predict coking properties and by-product yields with fair success from ultimate analysis. The coals which have proved exceptions to the general rules were found to have physical peculiarities. Run-of-mine Coal It must not be forgotten that run-of-mine coal is a composite material consisting of many constituents differing in physical properties and chemical analysis. A coal sample usually contains: 1. Glossy black coal known as anthraxylon or vitrain. This constituent usually has the strongest coking properties, and the lowest ash content. 2. Dull black coal consisting of attritus containing thin layers of anthraxylon. It is also known as clarain. This constituent, in a coking coal, usually has good to excellent coking properties. 3. Mineral charcoal or fusain. This is a porous black material which is soft and crumbly (unless impregnated with mineral matter) and which has absolutely no coking properties. It is different in every respect from the other constituents in coal. The volatile matter content of mineral charcoal is less than 20 per cent. even when it is associated with high-volatile coals. As would be expected the hydrogen content is low, and the carbon content is high. 4. A coal sample may contain tough gray canneloid material which has a high-volatile matter and a high hydrogen content, but is poor in coking qualities.

Jan 1, 1930

By E. A. Beck

(New York Meeting. February, 1913.) For a number of years many attempts have been made to use thermit in order to do away with piping in ingots. Some of these attempts were successful, while others did not give the expected results. Nearly every plant had its own method of using the thermit, and no special care was taken to study, the results or to find the causes for lack of success. Formerly the principle of the process was to decrease the piping by introducing a can filled with thermit, attached to an iron rod, into the head of the ingot directly after it bad been poured. In this case the thermit reaction took place in the upper part of the ingot, and it was thought that through the heat produced the head would keep liquid longer and piping thus be reduced. In other words, the aim was to keep the head of the ingot open by making use of the heat of the thermit reaction, which would thereby give the gases in the steel sufficient time to escape. This result can be attained by the application of a large enough quantity of thermit, but it would not be economical in general practice, and could only be used for high-grade material. Many steel-makers abroad and in this country have had this experience. The Th. Goldschmidt A. G., Germany, has, therefore, made a special study of this question with the co-operation of a well-known steel company, and has worked out a new method for. the application of thermit for this purpose. The results obtained have been most satisfactory and reliable, and this- process is now used in Germany on a large scale in many prominent steel-works.

Jan 4, 1913

By J. F. Blandy

In October last, I was call upon to examine a copper deposit in the South Mountain, near the Pennsylvania and Maryland boundary. The specimens shown me contained oxides and carbonates with native copper, and were similar to some that had been described to me some years ago as existing at the Luray Gap in Virginia. An examination of Rogers's Report on the Geology of Pennsylvania, led me to expect to see his so-called "Primal Formation," such as exists throughout the southeastern district of the State. I was therefore much surprised on arriving at the summit of the Western Maryland Railroad to find myself on familiar ground. Instead of the "Primal" as I had known it in Southeastern Pennsylvania, I soon decided that the rocks were identical with the ('Lake Superior Copper Formation." My visit was unfortunately a short one, —part of two days, and in that time I had to pass over a good many miles,—but I saw sufficient to convince me that instead of the Lake Superior Copper Formation being a local geological feature, it would have to be considered as a widely extended series of rocks. I was unable to even approximately estimate the thickness either of the trap zone or other members, schists and slates, of the series. In an article on the Copper 'Range of Michigan, prepared by C. P. Williams and myself in 1862, and published. in vol. xxxiv of the American Journal of Arts and Sciences, we endeavored to divide that range into zones, according to the character of the traps. The limited nature of the explorations at that time made this work very imperfect. Subsequent explorations have confirmed my notes then

Jan 1, 1879

By F. F. Sharpless

ARRIVING at Davis Junction, after leaving Portland, we expected to wait for an hour and a half, but found the superintendent of motive power of the Southern Pacific, Mr. Williams, waiting for us with a car, and were immediately taken aboard this and whisked off to Sacramento. After dinner, we were taken to the railroad shops to see their work in reclaiming scrap steel. We saw them draw off the slag from the electric furnace, and later make a casting. At about 11 o'clock, we took the train for Reno. A delegation of the Nevada Section, with Mr. Kirchen and Mr. Rives at its head, met us at the station. Immediately after breakfast, we started for the property of the Comstock Mines Co., where General Bulkeley Wells was to be our host. We had a de-lightful ride out to the mines and through the old city of Virginia, or through what was left of that old city, reaching General Wells' camp at about 10:30. This contains the newest thing in cyanidation and a remarkably fine iron and concrete mill building. After a trip underground, we were called to luncheon, where about 250 sat down. The afternoon was spent in the mill, and we were taken to Gold Hill, which is a part of Virginia City, for dinner, again as the guests of General Wells, who made a consummate toastmaster. Governor Emmet Boyle was the first speaker; he was followed by President Dwight, and then came President William Sproule of the Southern Pacific. A song, "The Engineer," was followed by Senator Key Pittman, Professor Jones of the State University, Mayor Stuart of Reno, and ex-Senator Charles Hend-erson. The president of the Western Pacific and the president of the Pacific Coast Line were there, also many notable operators of Nevada and California.

Jan 11, 1922

F. E. BACHMAN, Port Henry, N. Y. (written discussion*).-Experi-ments with titaniferous ores found in Essex County, New York, made by the MacIntyre Iron Co. in 1914, showed' that titaniferous concentrates are reduced in the furnace with no greater, and probably with less, expenditure of heat, and consequently of fuel, than non-titaniferous mag-netites; and as a greater proportion of their oxygen is removed by carbon monoxide than is the case with non-titaniferous magnetites, a lower fuel consumption for the reduction of iron may be expected. After the furnace was blown out at the end of the experiment, the formation in the hearth was found to be abnormal. The brickwork was replaced, entirely around the furnace, by a layer which at -the tuyere circle was made up of cinder, fine carbon, and coke; the coke, however, gradually disappeared toward the bottom, being replaced by cinder and graphite. The usual salamander of graphite and iron was missing. The material left in the hearth seemed to be cinder that had not drained from the last cast; its composition, though, would indicate that it was in the furnace previous to the taking off of the titaniferous ore. At first, this material was thought to be blast-furnace cinder mixed with less iron and graphite than is normal; but an examination showed it to be made up of cinder with small masses of iron and graphite. There were also patches of a steel-gray material having a metallic luster; a microscope showed these patches to be made up of black metallic crystals interlacing white crystals.

Jan 11, 1919

By Carl J. McHargue

Rods of 99.99 + pct Al which had initial orientatzons of <001>, <118>, <115>, <111>, and random were swaged at room temperature. Changes in orientation as a function of deformation were studied on axis distribution charts. The <001> orientation appeared to be relatively stable due to the inhomogeneity of the deformation process. near the <100> zone were quickly reoriented towards <001>. Orientations on the <110> zone between <118> and <115> appeared to be stable to reductions of about 50 pct, then were reoriented toward <001>. At very high reductzotzs. movement away from the <111> orientation was observed. the requirement that a circular cross section be maintained. In addition to these mechanical factors, there are grain-boundary effects in poly crystalline materials which are not yet understood. Hartmann and Macherauch conclude, for example, that multiple slip occurs for all orientations in fine-grained aluminum and copper and that the choice of operative slip systems has no simple relationship to orientation.? Many investigators have attempted to avoid problems of interpretation caused by an initial texture by treating the starting material to obtain as ran- IT has been generally accepted that the deformation texture obtained at high reductions, e.g. 90 pct, will not be noticeably affected by a prior texture; whereas, that obtained at reductions of 40 to 50 pct may be significantly influenced by the specimen history.&apos; Some recent studies, however, have been interpreted as showing that an initial texture strongly influenced the deformation textures in rods at reductions greater than 90 pct. Freda and Cullity suggested that the <001> texture in a heavily cold-worked copper rod was due to a <001> texture in the original casting. McHargue, Jetter? and Ogle concluded that the <001> component in an aluminum rod extruded at liquid nitrogen temperature was remanent from a <001> texture in the cast extrusion billet.3 Most of the published work on the effect of initial orientation on deformation textures has been for cold-rolled or compressed single crystals,4-6 The primary interest in these studies was to examine various orientations with regard to their stability under flow? thus determining the possibility of such orientations being stable end orientations. There appears to be no published studies on the effect of initial orientation on fiber textures in polycrystalline specimens. A recent study, however, is concerned with the reorientation of individual grains in polycrystalline specimens pulled in tension.? Although the reorientation of single crystals loaded in simple tension is well known, the movements in the forming of wires and rods would be expected to be different due to the circular array of radial-compressive stresses exerted by the die walls or the rolls, and to

Jan 1, 1962

By David E. Hyatt

The chemical attributes of cyanides have long been exploited in ore pro- cessing schemes for the recovery of copper, molybdenum, gold, silver, and other metal values. Blast furnacing operations are significant unintentional producers of cyanides which find their way into process waters. Many of the more than 20,000 electroplating facilities in the United States utilize cyanide plating baths and generate cyanide containing wastes. As social, political, and economic pressures for water quality attainment, maintenance, and preservation grow, the requirements for the development of treatment technology to control cyanide levels in wastewater become increasingly apparent. Just as the chemistry of the cyanide ion 1s an integral part of its industrial applicability, so must this chemistry be a fundamental part of any decomposition or removal technology used to control its level in effluent or recycled waters. The complexity of this chemistry is substantial and it cannot be considered in a superficial or cursory manner if control system design is to be both efficient and reliable.

Jan 1, 1975

By AIME AIME

As already announced in the January Bulletin, this publication will be issued during the coming year monthly instead of bi-monthly as heretofore. Among other reasons for this change, it is desired to effect thereby the earlier transmission to members of important papers, lists of candidates for membership, and other items of timely information. Spokane Meeting and Excursions. Further details of the 97th meeting of the Institute have been sent to members in the Circular of May 8, 1909. The list of those intending to go on the excursion is filling up, and since preference in position of state-room or berth is given in the order of application, members and guests who expect to accompany the party and have not yet communicated with Mr.. Theodore Dwight, 29 West 39th St., New York, N. Y., are earnestly requested to do so without delay. For convenience of the members a summary of the additional information is here presented. A special train of Pullman cars will leave Chicago about September 15. This train will be side-tracked at all places visited, and the sleepers will be available for lodging and the dining-car for meals during the entire trip, except during the Yellowstone Park tour. The general cost of the trip per member will be $300, which includes transportation, berth, and meals for the entire trip from Chicago back to Chicago, almost 6,000 miles, and the tour through. Yellowstone Park, occupying in all about 30 days. Special, accommodations on the train will be furnished at the following rates

Jun 1, 1909

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By J. A. Thompson, M. A. Mayers

IN recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.1-14 Only in Russell&apos;s method11 and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce-the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼ in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C. consisting of two annuli of 0.011-in. (0.28-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.&apos; The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-&apos; cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher&apos; has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher&apos;s analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher&apos;s but with fewer assumptions has been given by Whipple.&apos; In contrast to Fisher&apos;s analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm&apos;; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler&apos;s lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By A. K. Sinha

The annual production and productivity of underground coal mines in recent years declined from 334 Mt (368 million st) and 14.5 t (16 st) per man per shift in 1969 to approximately 254 Mt (280 million st) and less than 8 t (9 st) per man per shift in 1977. Productivity is still hovering at about 7.25 t (8 st) per man per shift. According to US Bureau of Mines, the estimated US coal reserve is about 396 Gt (437 billion st), 68.65% of which is obtainable by underground mining methods. Approximately 153 Gt (169 billion st), or about 85.2% of the high Btu premium coking coal of the eastern US, would need to be extracted by underground mining methods. It is thus apparent that under- ground mining will continue to play a major role in total US coal production, which is expected to rapidly increase to about 1.1 Gt (1.2 billion st) by 1985, with about 606 Mt (668 million st) being contributed by underground mines. Production Potential of Continuous Mining The production potential of a continuous mining section depends primarily on the producing ability of the miner, transporting ability of the face haulage, and the matching of the two systems. The producing ability of the continuous miner depends on its actual cutting ability and the time available for cutting coal. The performance of 10 continuous miners operating in coal seams of various thicknesses were monitored in Pennsylvania and West Virginia, using continuous electrical power analyzers and time studies. The recordings on current and power strip charts yielded an accurate analysis of the cutting, trimming, and idle times of the machines on a full shift basis. Continuous miners of various models and sizes from 112-298 kW (150-400 hp) were monitored. Based on actual cutting time, the average cutting ability of the machines, as shown in [Fig. 1], ranged from

Jan 1, 1983

By Valentin R. Garfias

The world&apos;s petroleum production in 1929 is estimated at 1,479,335,-000 bbl., which represents an increase of about 157,000,000 over 1928, as compared with an increase of 61,000,000 bbl. in the previous year. During the present year a more definite policy of conservation has been seriously considered by the foremost executives of the companies controlling the bulk of domestic and foreign production, and the United States Government has taken an active interest in the development of this program. Definite steps have already been taken and the industry is gradually establishing a foundation for closer and more intelligent cooperation. The entire program, however, is still in a formative or experimental stage. Among other salient constructive steps may be mentioned the establishing of tentative agreements of unification in the price of oil products exported from the United States, the putting into effect of a gas conservation law in California, and the marked tendency towards consolidatlions of the various branches of the industry into larger units. The publication of the draft of the proposed petroleum law in Colombia and of the Mexican Labor Law, on the other hand, has created papre-hension and uncertainty. It is confidently expected, however, that these perliminary drafts will be materially modified before the laws arc promulgated, or otherwise they may destroy the interest they are intended to protect. United States Production in the United States, which remained stationary during 1927 and 1928, increased about 105,000,000 bbl., or 11.6 per cent. This increase is due primarily to deeper drilling in the California fields and to the discovery of new pools in Texas and Oklahoma. The progress of the conservation program was marked by the action of the Government in stopping further permits to drill on Government lands; by putting into effect early in September the California Gas Conservation Law, and by

Jan 1, 1930

By John M. Lovejoy

I take pleasure in transmitting herewith "Petroleum Development and Technology in 1927," in which we have attempted to set out in a series of 40 papers with attendant discussions the advances made in Production Engineering and Refinery Engineering during the year. The volume also contains a digest of round table discussions on Petroleum Engineering Research problems and Petroleum Engineering Education. In addition to the above we set out in 16 papers a review of production of each producing area of the United States and of the more important foreign countries, together with a review of the world&apos;s production and forecasts for 1928. We also include 8 papers on the Economics of the oil industry. The papers and discussions included herein represent the contributions of more than 200 engineers, including the foremost in each line. These papers were presented at technical sessions held in Fort Worth in October, 1927, and at the annual meeting in New York in February, 1928. We desire to express our thanks and appreciation to all those who have contributed to this volume. As in previous years, we have attempted to emphasize the value of both written and impromptu discussions. -We have made a practice of returning all impromptu discussions to the authors for correction and amplification, and because of this practice we feel that the discussions contained herein are in very presentable and readable form. It was decided by the nominat,ing committee when meeting for thc purpose of nominating officers for 1928 to eliminate the vice-chairrnanship for Transportation Engineering, as that branch of the industry seemed to come more naturally under the activities of the American Petroleum Institute. It was also decided by this committee to institute a new vice-chairmanship for Petroleum Engineering Research. Wc have had heretofore round table discussions on engineering research, but through the newly created vice-chairmanship, to which Mr. L. C. Uren was elected, we expect to have more comprehensive sessions on engineering research than heretofort.

Jan 1, 1928

On Dec. 8, 1916, at a meeting held at the Massachusetts Institute of Technology, the John Fritz Medal was presented to Professor Elihu, Thomson, "for his achievements in electrical invention, in electrical engineering, in industrial development and,in scientific research." Professor Albert Sauveur presided. John J. Carty, chairman of the Presentation Committee of the Board of Award, made a short address-on the history and significance of the medal. He was followed by E. W. Rice, Jr., president of the General Electric Co., who spoke at length of the achievements of Dr. Thomson, whom he called "one of the world&apos;s most prolific and industrious inventors and scientists." Among other things, he said: "In the, field of electrical inventions alone, Professor Thomson has been awarded something over 550 United States patents, and in other fields; notably mechanical work, about 150 patent.,. he has made contributions to the world&apos;s scientific, and technical literature, in several hundred articles describing not only his own dis-coveries and inventions but making remarkably interesting contributions to scientific speculation and thought. "A skilled workman, he is always able himself to do the work which he asks others to perform. "His inventions are the result of such profound and accurate knowledge,. and developed with such skill, that they almost invariably work on the first, trial in accordance with expectation." Dr. Richard C. Maclaurin, President of the Massachusetts Institute of Technology, spoke of the personality of the man as well as of his accomplishments, as follows: "He has not only clone great things himself, but has shown ,in intense desire to help all who are struggling earnestly with scientific problems. He has proved an inspiration to an ever-widening circle of engineers and others who have entrusted him with their secrets and sought his help in overcoming their difficulties. They have done this knowing. that they had only to ask in order to get the full benefit of his

Jan 2, 1917

By W. A. Ver Wiebe

The year 1940 was singularly unmarked by sensational developments in Kansas. Routine operations were carried on in a systematic, orderly fashion and the efforts of oil producers were concentrated on extending known fields. In Kansas an arbitrary yardstick for wildcats has been set up. A well drilled mile or more from a known pool or well is now considered a wildcat. A "rank wildcat" is one that is drilled at least 2 miles from any known producer. During 1940, rank wildcats resulted in the completion of 116 test wells, among which 16 were successful in finding new oil pools and the remaining I00 were dry holes. The ratio of successful wells to dry holes, therefore, was approximately I:6. During the year, 1890 wells were completed in eastern and western Kansas. This figure is somewhat lower than that given in several trade journals, because it does not include wells that were deepened or wells that were recompleted in a different geological horizon. About three fourths of these (1423) were completed as commercial oil wells (I220 in western and 203 in eastern Kansas). The commercial gas wells completed number 58 of which 10 are in eastern Kansas and 48 in western Kansas. Of the remzining completions 147 are dry holes in eastern and 262 are dry holes in western Kansas. Based on daily potential capacity, the new discoveries of the year account for a cumulative initial production of 46,000 bbl. in eastern and 2,128,000 bbl. in western Kansas. The state of Kansas attained a new peak in production, with the total of 66,245,000 bbl. for the year 1940, the number of contributing wells being 20,779. Thus the increase over 1939, when about 58 million barrels was produced, is considerable. The previous peak occurred in 1937, when 70,761,000 bbl. was marketed. In another still earlier peak, in 1917, slightly more than 45,000,000 bbl. was produced and sold. The production of gas probably reached a new peak also during 1940, with its total of 85 1/2 billion cubic feet. Between the peak of the year 1908, when over 80 billion cubic feet was produced, and that of 1940, the production dropped to a low point of 16 billion cubic feet in the year 1921. The number of test wells drilled was larger than in 1939; that is, 1890 compared with 1458. The first peak was reached in 1904, when 2782 wells were drilled. The number dropped off rapidly, to 368 three years later, but rose to the second and highest peak in 1918, when 4671 test wells were completed. In the period between 1904 and 1912 more gas wells were completed than oil wells. Between the high peak of completions in 1918 and somewhat lower peak of 1937, the low point was reached during 1931, with the completion of only 470 test wells. In the number of new pools discovered, Kansas again ranks high among the states. The exact number depends somewhat upon the interpretation of a "new" area— whether it should be called a new pool or a long extension of an old pool. Unfortunately, the matter of securing the right kind of production allowable also enters into this question. Often the decision regarding a new pool cannot be made until other wells

Jan 1, 1941