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By A. Mitchell, M. Etienne

VARIOUS'-3 reports on the electroslag remelting process refer to the "thin skin of slag" existing around the slag pool and the solidifying ingot, but none considers the various mechanisms by which this layer forms and thus influences the surface quality of the ingot. A vertical section4,5 of the Cao-CaF2-Al2O3 diagram is shown in Fig. 1 between CaF2 and 6Al2.CaO3 From this, it is seen that a typical "70:30" CaF2:A1a3 slag will solidify to produce 6Al2O3.CaO primary phase in a eutectic matrix. The commercial slags contain sufficient CaO to produce* this composition by both the

Jan 1, 1969

By M. Hayri Erten

In this research the possibility of pelletizing high grade fluorsoar fines or flotation concentrates with the use of calcined colemanite as binder is investigated, and the room temperature and elevated temperature strengths of these pellets are compared with those of pellets which are obtained by using bentonite as binder. Pellets of 10-12 mm. size and having 10% calcined colemanite showed a much higher room temperature strength than those containing 5% benonite, both being endurated at 1000°C for 15 minutes. However, when the same batch of pellets were tested at elevated temperatures of 250º to 500°C, bentonite gave better results. X-ray tests showed that in the pellets endurated at 1000°C for 15 minutes the original crystal structure of fluorite mineral is preserved.

Jan 1, 1977

By William G. Pariseau

The extraction ratio approach to pillar design in flat seams is based on a mathematically exact analysis that is a reasonable physical approximation to room-and-pillar layouts in many instances. The essentials of the approach are reviewed and then mathematically approximate formulas for pillar design in inclined seams of arbitrary dip are proposed. Detailed numerical analysis of stress about a typical 5 entry, 4 pillar panel at dips of 0, 15, 30, 45, 60, 75 and 90 degrees at low and high extraction ratios show that the proposed inclined seam extraction ratio formulas for pillar normal and shear stresses, although conservative, have an accuracy quite adequate for engineering purposes. Appropriate pillar safety factors for compressive and shear failure and a safety criterion for overturning are specified.

Jan 1, 1982

By Charles L. Elliot

Worldwide manpower utilization reached a new high at 10,482 professional man-months and expenditures increased to $19.9 million for mining geophysical activity during 1965. This is up from 9323 man-months and $14.5 million in 1964. Worldwide geophysical activity measured in percent distribution of the total manpower utilization and expenditures is presented in the accompanying Figs. 1 and 2. In terms of the total manpower utilization, ground surveys accounted for 61%, airborne surveys 18%, and mining geophysical research activity 21%. For expenditures, the breakdown was ground surveys, 49%; airborne surveys, 3901o; and research, 12%. Industry was responsible in general for 74% of the manpower utilization and 80% of the expenditures. Manpower costs in 1965 averaged $1900 per professional man-month.

Jan 11, 1966

By EDBIUND U. NORTH

IN making a glass model of mine-workings, each mine will present some little individualities, to meet which will call for the exercise of special ingenuity. Having made several models, I offer the following details of the model of the Montana-Tonopah mine-workings, believing that with small changes for different conditions the method described can be successfully used in making a glass model of the workings of any mine. The model, Fig. 1, has the top, one end, and the front removed. The case is made of kiln-dried pine, painted with several coats of dead-white paint. It is made to take sheets of glass 24 by 42 in. in size, and is 18 in. high, the workings shown being on a scale of 1 in. = 40 ft., or 4800 : 1 scale. The base is made of four pieces of 2-in. material, well pinned and glued together. The back, of material 1 in. thick, is secured rigidly to the base by screws and countersinking. The four posts, 1.5 in. square, are so cut that. the front and two ends of the model fit in flush with the outside edges of the posts. The top rails, 1 in. square, are fastened rigidly to the front and back posts by means of small iron braces. The ends, front, and top of the case are of 0.5-in. material; the ends and front are held in place at the bottom by pegs fitting into the base ; at the top the ends are held by buttons and the front by cupboard-hooks on the inside. Hinged hasps on the cover, fitting over staples in the end-pieces, make it easy to lock the entire case. Before the back is fastened to the base, it is cut with horizontal and vertical grooves to receive the horizontal and vertical sheets of glass, shown clearly in Figs. 1 and 2. The horizontal grooves, spaced to scale, represent the vertical distances between the levels at the shaft. The vertical grooves are placed wherever cross-sections of the workings are desired.

Jan 1, 1910

AGGLOMERATION U.S. 4,067,727 - In the sintering of a charge of iron oxide ore, a fuel and a flux on a travelling grate machine, the dust problem is minimized by providing a plurality of cooling zones and by directing heated dust-laden air from a first cooling zone to the sintering zone wherein the dust is filtered from the air by the material being sintered. Air from a further cooling zone can be exhausted directly to the atmosphere. Dust removal in the cooling zone is improved by using a purging zone in which higher pressure air agitates the dust in the sintered material. This patent is a division of U.S. Patent No. 3,973,762, dated Aug. 10, 1976. F. Cappel, assigned to Dravo Corp. Jan. 10, 1978. 6 pp. (75-5). Filed: 4-1-76 (672,748).

Jan 1, 1979

US underground mine production of nonfuel minerals was 153 million tons of crude ore in 1971, according to a recent US Bureau of Mines report compiled by Dravo Corp. Underground capacity includes all nonfuel mineral commodities and is distributed into three general categories: (1) metallic ores; (2) nonmetallic ores; and (3) construction materials, such as clay, sandstone, and limestone. All three categories are produced by a combination of open-pit and underground methods. While US underground mining represents only 5.9% of total domestic capacity, it is significant in the types of products produced. Domestic supplies of potash, trona, A lead, zinc, sulfur, and fluorspar are almost exclusively recovered from underground mines, as well as a significant portion of the gold, silver, molybdenum, and salt supply.

Jan 7, 1975

By AIME AIME

THE Petroleum Division held a very successful meeting in Los Angeles, Oct. 4 and 5. The meeting was held on the eighth floor of the Chamber of Commerce building, the first day being devoted to technical sessions. Seventy-five members were registered before the opening of the first session. Glenn D. Robertson, vice-chairman of the local section, opened the meeting and introduced Edwin Higgins, managing director of the California Oil and Gas Association, who gave an interesting talk on the recently enacted gas conservation law in California. He explained that the law is an experiment which will be watched with a great deal of interest. The purpose of the law, which went into effect on Sept. 1, is to curb wastage and over-production of gas,

Jan 1, 1929

By Freeman Bishop

Quietly picking his way through the thorny thicket of conservation issues is William E. Ruckelshaus, director of the Environmental Protection Agency in which President Nixon gathered the various anti- pollution units from the Interior, Commerce. Agriculture and Health. Education and Welfare departments. Mr. Ruckelshaus. EPA's first administrator, moved over from being Assistant Attorney General in charge of the civil division at Justice to this new post. Essentially, EPA is charged with administering swiftly proliferating antipollution programs. This means policing industry cities, farms and everything else. Ruckelshaus has been quietly fitting together the various pieces of this new agency, pulling then1 out of other Federal departments. Some 5800 employees are involved. The budget in 1971 for these segments will total about $1.5 billion.

Jan 1, 1971

By E. Lifshin, R. E. Hanneman

QUANTITATIVE applications of the electron micro-beam probe frequently involve the evaluation of complex mathematical expressions and/or the analysis of large amounts of experimental data. The purpose of this communication is to describe briefly a versatile and useful computer program system that is applicable to analyze rapidly a wide variety of practical microprobe problems. This system consists of a group of ten FORTRAN programs that can be stored on tape, cards, or in the memory disc of the computer. These programs, or links, can be run individually or in any prespecified sequence without interrupting the operation of the computer or without destroying information which is being transfered from one link to another. For the program system described here a GE-235 computer with disc storage was used, so that the DCHAIN method of program linking was employed. Included in the library are programs to: 1) initiate analysis of a new set of data and transfer control between all other programs in any predetermined manner; 2) generate theoretical calibration curves of composition vs relative intensity; 3) generate empirical deviation parameters from least-square fits of experimental calibration data from standards of known composition; 4) convert raw X-ray data to corrected composition; 5) determine inter diffusion coefficients by Matano analysis of con centrat ion -distance data on a uniaxial diffusion couple; 6) determine activation energies and frequency factors of temperature-activated processes such as diffusion; and 7) generate calibration curves for determination of the thickness of thin films using microanalysis. A detailed description of these computer programs and their underlying principles is available on request from the authors."' The first program to generate theoretical calibration curves of corrected relative intensities vs composition uses the Poole and Thomas atomic number correction' and the Philibert absorption factor' with a voltage-dependent mass absorption coefficient for electrons in the alloy. A modified Castaing fluores- cence correction is also used which includes the effects of both Ka and KO radiation and over voltage.' Once the theoretical curves have been calculated in 1 wt pct intervals, these results are least-squares fit to obtain Ziebold deviation parameters' which are stored in COMMON in the computer memory. The net discrepancies between the original theoretical calibration curve and the regenerated curve using the Ziebold parameter are computed. Although this link is explicitly written for K-K fluorescent interactions, it can be applied to K-L, L-K, and L-L interactions as previously disc~ssed."~ Similar programs have also been written to utilize the Wittry fluorescence correction, Birks combined corrections, and various other corrections.' These modified programs have proved to be quite useful for quantitative comparisons of the results of the various theories. The program for conversion of raw X-ray data to corrected composition includes corrections for drift, backround, and instrumental dead time. The corrected intensities are converted to composition by use of the Ziebold equation"2 and parameter obtained from the program system. The results can be obtained for either atom or weight fractions. In addition to accurately computing interdiffusion coefficients the Matano analysis program calculates least-square smoothed values of concentration, concentration gradient, and curvature for each point on the raw input concentration profile. In order to obtain high accuracies a unique method of performing a least-square polynomial fit to incrementally advancing profile segments which overlap is used.' This program has been successfully modified for use in ternary diffusion problems3 and can readily be modified to handle analysis of diffusion profiles which include phase boundary discontinuities. This link is generally applicable to analysis of interdiffusion data obtained by other techniques as well as by the microprobe. The primary function of the next program is to least-squares fit experimental diffusion data to the normal Arrhenius function: D = Doexp(-Q/RT), to obtain values of Do and Q. In addition the probable error and one, two, and three u statistical confidence limits of DO, Q, and log D are evaluated. This program is also directly useful for analysis of any other simple temperature-activated processes including conductivity, and certain deformation and chemical processes. The program to generate calibration curves for film-thickness determination using the microprobe is based on a numerical integration of the equation derived by Cockett and ~avis.' Values of film thickness obtained by this program for copper on various substrates are in good agreement with measurements made by other techniques. Versions of the above program system have been prepared for use with or without a remote teletype connection to the computer for processing on either a real-time or time-share basis. The instrumentation coupling a microprobe to a teletype for automatic data collection and analysis by the presently described program system has been reported elsewhere by the authors.' If teletype equipment is not used to communicate with the computer, standard methods of card reading and tape reading can be used. In either

Jan 1, 1967

By D. Gupta, S. Weinig

This investigation comprises the study of dislocation-oxygen interactions in a! titanium and its effect on the ductile to brittle transition in titanium. Internal friction techniques using a low-frequency lorsion pendulum were used to study the oxygen atom interactions with dislocations in "superpurity" titanium. A calculation of the interaction energy between an oxygen atom and a dislocation, based on the "breakaway" strain resulted in a value of 0.015 ev as compared to theoretical values of 0.022 and 0.035 ev for edge and screw dislocations, respectively. Both the saturation of the room temperature decrement and the transition from ductile to brittle behavior occurred at 1.5 at. pct 0. It was proposed that the embrittlement was due to oxygen atoms immobilizing the dislocations. It was possible to increase the ductility of the Ti-0 binary alloys by decreasing the oxygen pinning. The increase in uniform elongation was 30 pct for an increase in the preanneal temperature of 300°C. ThE room-temperature ductility of a titanium is significantly affected by interstitial solutes. Although oxygen has a solid solubility of 15.5 pct by weight, the room-temperature ductility extends only to 0.6 pct.' The ductility precipitously falls at this concentration and the fracture characteristics change from ductile to brittle.2 The small effective bulk composition of solute required to destroy the room-temperature ductility of the titanium must be indicative of an in-homogeneous distribution of solute atoms. Internal friction techniques were used in this investigation to

Jan 1, 1960

By S. G. Bankoff

INCE1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. [ ] In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (-200 mesh) and 50 c.c. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments [c] through g are more insoluble than lead carbonate, therefore should prevent the formation of lead carbonate on the galena surface. In experiment [i] the calcium oxalate, which presumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments [j] through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1941

By S.G. Bankoff

Ince1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (—200 mesh) and 50 C.C. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments c through g are more insoluble than lead carbonate, there- fore should prevent the formation of lead carbonate on the galena surface. In experiment i the calcium oxalate, which precumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments j through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1943

By S. G. Bankoff

Ince1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (—200 mesh) and 50 C.C. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments c through g are more insoluble than lead carbonate, there- fore should prevent the formation of lead carbonate on the galena surface. In experiment i the calcium oxalate, which precumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments j through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1943

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of' cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi'e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600'F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.' Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.'-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors' laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:'-'' the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

By S Bankoff

INCE1 proposed that electrostatic attraction between oppositely charged particles was responsible for slime-coating. Del Giudice2 postulated the metathetic formation of a cementing compound. Wark3 suggested that prevention of slime-coating was related to peptization of the slime. [ ] In the experiments of Table I the technique employed was essentially that of del Giudice, with the difference that the particle was examined under a film of water rather than dry.4 In general, the polished particle was agitated for 2 min. in a pulp consisting of 12.5 grams of the slime (-200 mesh) and 50 c.c. of distilled water, washed in three baths of distilled water, and examined at 220 diameters with the Leitz Ultropak. Observations of Brownian movement were made at 850 diameters with dark-field illumination. Several of these experiments do not jibe with the metathesis theory. According to published solubilities,5,6 the lead salts of the anions in experiments c through g are more insoluble than lead carbonate, there- [ ] fore should prevent the formation of lead carbonate on the galena surface. In experiment i the calcium oxalate, which presumably was on the calcite surfaces, should have permitted the formation of a lead carbonate cement by virtue of its greater solubility. Experiments j through m show that the addition of lime accelerates the deposition of quartz onto a galena surface. The writer is unable to postulate a satisfactory cementing compound, according to the metathesis theory, to explain this effect. These experiments led to the conclusion that the metathetic formation of a cement-

Jan 1, 1941

By F. A. Hill

Coal mining in the State of Washington offers many interesting problems for the mining engineer, due to the varied physical conditions occurring in different fields, and often in, the same mine. The different coal seams worked in the same mine commonly require different mining and transportation methods for economical operation. The coal measures have inclinations ranging from 5° to vertical, and in the same mine the dip of the coal may vary from 30° to 50°. In all fields, the seams are extensively faulted, folded, and sheared. The quality of the coal produced ranges from brown lignite to bituminous- coking coal, the following being typical analyses: Lignite Sub Coking Coal bituminous Moisture 23.5 14.30 0.57 Volatile hydrocarbon 31.0 33.03 23.57 Fixed carbon 37.4 41.30 65.55 Ash 8.1 11.37 10.31 100.0. 100.00 100.00 Very little of the coal contains as much as 0.75 per cent. sulphur. The brown lignites occur mostly in Lewis and Thurston Counties, and, as a rule are very cheaply mined. This coal has been successfully used in locomotives of the Oregon & Washington Railroad, after equipping them with specially designed fireboxes. The sub-bituminous coals occur in all the coal-mining counties. Their cost of production varies widely, according to the character of the formations, the pitch, and the wall conditions. This makes a fairly good steam coal, but the lump is used mostly for domestic trade, after grading into lump, nut, and pea.

Jan 4, 1918

By W. T. Lundy

THE forms in which sulphur is commonly found-native sulphur, sulphides of many metals and sulphates-are widely distributed throughout the world. The two first mentioned are the principal sources of sulphur. Substantial amounts of sulphur in some form are recovered from gases from industrial plants and from gases from smelters treating other minerals. In recent years, plants have been installed in the United States to recover sulphur in elemental form from sour gases."' The amount of sulphur so produced is small at the present time but undoubtedly will increase in the future. The recovery of sulphur from gases is not covered in this chapter, which is confined to: (1) native sulphur deposits of Texas and Louisiana; (2) those of Italy; (3) other scattered deposits of native sulphur; and (4) pyrites deposits found in many countries of the world.30 Sulphur, a nonmetallic element, occurs normally in well developed bipyramidal or tabular crystals of the orthorhombic system, as well as in stalactitic and earthy masses. The mineral has a distinctive yellow color, which may be dark and discolored by impurities; the streak is white; the luster is resinous; and the fracture is conchoidal to uneven. Sulphur is translucent to opaque; has a hardness of 1.5 to 2.5, a specific gravity of 2.05, and an atomic weight of 32.06.16 The molecular weight of the solid is expressed by the symbol SS and that of the liquid and vapor ranges from S2 to S8, depending on the temperature. Sulphur melts at a temperature between 2340 and 248°F, depending on its crystalline state, to a liquid of dark amber color, the boiling point of which is 832°F. The viscosity near the melting point is about that of water and increases to 50,000 times that of water at a temperature of 380°F, subsequently falling rapidly to a low figure at the boiling point. Crystallization changes slowly from rhombic to monoclinic above 205 °F and in cooling the transformation is reversed. The mineral is a very poor conductor of heat and electricity; it is insoluble in water and nearly all acids and is soluble in cold carbon bisulphide and carbon tetrachloride. It ignites in air at a temperature of 478°F, burning with a distinctive blue flame with evolution of sulphur dioxide.47

Jan 1, 1949

By F. A. Veer, W. G. Burgers, B. H. Kolster

Starting-- from Cu-Si diffusion couples a study of diffusion in the intermetallic compound Cu3Si of the Cu-Si system has been made. Mmker experiments showed copper to be the diffusing element. From the rate of growth of the Cu3Si phase diffusion coefficients were derived. The activation energy for diffusion is 18.6 kcal per mole. The couples show some interesting microscopic features, for which a tentative explanation is given. THE synthesis of dimethyldichlorosilane, (CH3)2SiC12, an important compound in the manufacture of methyl-silicones, takes place at the surface of a thin Cu3Si layer deposited on a mass of silicon particles."' By passing CH3C1 vapor at about 350°C, silicon atoms are consumed from Cu3Si in forming the volatile silane molecules, thus leaving copper atoms at the surface. It is well-known that copper acts as a poison for the above-mentioned reaction by catalyzing the dissociation of methylchloride.' However, no poisonous effect is observed, at least not before most of the silicon from the particles is converted into silane.3 This would be understandable, if either the copper atoms diffuse through the Cu3Si deposit to the underlying silicon or silicon atoms diffuse in the reverse direction to the copper, both processes resulting in the formation of new Cu3Si and so ensuring the proceeding of the reaction. In this paper experiments are described, demonstrating copper to be the diffusing element. Also a very low activation energy for the diffusion is observed. EXPERIMENTAL The silicon used contained 1 ppm Mg and 1 ppm Cu; the copper was spectroscopically pure (Fe: 2 ppm; Ag, Mg, Si: 1 ppm). The copper and silicon samples were prepared in the form of blocks of approximately 10 by 10 by 5 mm with two parallel sides by spark-machining. The blocks were ground on emery paper (grit 600), etched (copper with nitric acid, silicon with a 4:l nitric acid:hydrofluoric acid mixture), and cleaned with alcohol. As the brittleness of the silicon did not allow a welding procedure to prepare the diffusion couples, the copper and silicon blocks were pressed together in a steel clamp. The pressure exerted by the clamp brought about contact between the parts of the couple and so ensured proceeding of the diffusion. The couples were heated in a vacuum furnace (about 10"5 Torr). The temperature was stabilized within 1 pct. After a heat treatment a section parallel to the direction of diffusion was examined in the microscope and in the X-ray scanning microanalyzer. To determine whether copper or silicon is the diffusing element marker experiments were carried out using tungsten wires with a 20-p diam. EXPERIMENTAL RESULTS Figs. 1, 2, 3, and 4 give micrographs of diffusion zones of Cu/Si couples. Analysis by the electron mi-croprobe of the Cu/Si samples after a definite heat treatment revealed the existence of only one intermetallic phase as can be seen from the line scan shown in Fig. 5. From the X-ray diffraction pattern it could be deduced that this phase was CU 3 Si.4 Even when diffusion zones of considerable width (up to 600 p) were obtained, no other phases occurring in the Cu-Si system could be detected, neither by the electron microprobe nor by X-ray diffraction analysis. The optical anisotropy of the Cu3Si phase made it possible to observe the columnar shape of the crystal-

Jan 1, 1969

By G. Thodos, R. B. Grieves

A method has been developed For predicting the critical temperatures and critical pressures of binary mixtures of carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen with the normal paraffin hydrocarbons. For carbon-dioxide and hydrogen-sulfide systems, relations are presented that take into account the peculiar behavior of mixtures with closely boiling components, such as carbon dioxide-ethane and hydrogen sulfide-propane mixtures which exhibit minimum critical temperature points. For hydrogen, nitrogen and carbon-monoxide systems, the extreme critical behavior caused by wide differences in pure component properties is established In addition, those fixed gas-paraffin systems which resemble paraffin-paraffin systems are also accounted for. For a mixture of known composition, the pure component critical temperatures, critical pressures and normal boiling points are all that are required to determine its critical point. Graphical relations are presented relating Tc and PC , of the mixture to the pure component properties. From the treatment of 12 carbon-dioxide and hydrogen-sulfide systems reported in the literature (74 mixtures), the expected error lor the critical temperature is approximately 1.5 per cent, and for the critical pressure, approximately 2 per cent. From the treatment of six hydrogen, nitrogen and carbon-monoxide systems reported in the literature (30 mixtures), the expected error for both the critical temperature and critical pressure is approximately 2.5 per cent. The relationships, which have been developed with only normal paraffins as the hydrocarbon components, may be extended to those isoparaffins and olefins which fall within the allowable volatility ranges. INTRODUCTION Many of the fixed gases — carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen — occur in natural mixtures with hydrocarbons. Carbon dioxide and hydrogen sulfide are frequent components of the fluids produced from underground petroleum reservoirs. Nitrogen, carbon dioxide and hydrogen sulfide are present in varying quantities in most natural gases and gas-condensate well effluents. Hydrogen mixtures are of considerable interest in many phases of refining processes of petroleum. The determination of the critical temperatures and critical pressures of such mixtures is of value in vapor-liquid equilibrium studies, for the prediction of the characteristics of underground reservoirs, and for reduced-state correlations of PVT, transport and thermodynamic properties. The accurate estimation of the critical point for binary mixtures is an important initial step toward a complete analysis for the establishment of the critical temperatures and pressures of multi-component mixtures. Methods for predicting the critical temperatures and critical pressures of binary hydrocarbon systems have already been presented in the literature.8 It is possible to apply these existing methods to fixed gas-paraffin mixtures, but due to their unusual critical behavior, values calculated deviate considerably from experimental values. For systems containing trace quantities of the fixed gases, these methods are acceptable; however, for systems containing more than 5 mol per cent of the fixed gases, these utterly fail to produce reasonable critical values. Consequently, in this study a method has been developed for handling such binary mixtures over the entire composition range. CARBON-DIOXIDE AND HYDROGEN-SULFIDE SYSTEMS The critical behavior and the vapor pressure behavior of mixtures of carbon dioxide and hydrogen sulfide with paraffinic hydrocarbons may be quite similar or quite dissimilar to that of paraffin-paraffin mixtures, depending on the volatilities of the components involved. The critical temperature and normal boiling point of carbon dioxide are very close to the corresponding values for ethane, while its critical pressure is considerably higher than that of ethane. The normal boiling point of