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Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By George S. Rice

The subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on blimps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free from folding and faulting. Definition of Bumps Bumps in coal mines, as defined in this paper, are sudden violent bursts of coal that usually occur without warning in the extraction of pillars and may or may not be accompanied incidentally by falls of draw slate, upheaval of bottom and smashing of timbers. They are not known to occur where the advancing longwall method of mining, accompanied by

Jan 1, 1936

By George S. Rice

The subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on blimps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free from folding and faulting. Definition of Bumps Bumps in coal mines, as defined in this paper, are sudden violent bursts of coal that usually occur without warning in the extraction of pillars and may or may not be accompanied incidentally by falls of draw slate, upheaval of bottom and smashing of timbers. They are not known to occur where the advancing longwall method of mining, accompanied by

Jan 1, 1936

By K. Takahashi, I. Iwasaki

The methyl stretching vibrations for a series of normal xanthates, isoxanthates and normal amines were determined with the aid of an infrared spectro-photometer, and the results were compared with published information on the corresponding alcohols. The frequency shifts of methyl stretching vibrations may be attributed to the inductive effect of polar groups. The hydrogens in the shorter chain alkyl groups are somewhat polar and can be expected to interact with water molecules by hydrogen bonding. Contact angle, surface tension lowering, solubility, and critical micelle concentration appear to be related to the induced polarity of the alkyl groups. Traube's rule states that in homologous series of compounds solubility decreases and surface activity increases regularly with the size of the hydrocarbon group. Analyzing the work of transfer of a solute from solution to surface, Langmuir' interpreted this rule to mean that each CH2 group added to a molecule produced its effect independently of the others. It is also well known2 that the maximum equilibrium contact angle with sulfhydryl collectors is independent of the polar groups and of the sulfide minerals, and that it increases to a certain limit with the number of carbon atoms in the alkyl group. This observation is thought to demonstrate the orientation of the collector molecules at the sulfide surfaces. The dependence on the hydrocarbon chain length is usually explained as due to the screening of the force field of polar mineral surfaces.3-5 Here again, Langmuir's principle of independent surface action appears to be implied. Heteropolar compounds consist of nonpolar and polar groups, the former being the hydrocarbon group and the latter containing such electronegative atoms as O, N, S, P, or halogens. According to Palit6 the hydrogens in the alkyl groups are more electroposi- tive than in the paraffins owing to the negative inductive effect of the polar groups and a possibility that a hydrogen bond with water molecules ensues. Goto and Takenaka7 provided direct evidence of the inductive effect by measuring the shift of the C-H stretching vibrations of alcohols, acids, and alkyl bromides with an infrared spectrophotometer. Their approach appeared to be directly applicable to the studies of surface activity both at air-water and water-mineral interfaces encountered in flotation systems. The present article attempts to relate the C-H stretching vibrations of alkyl xanthates, alcohols, and amines with such flotation chemistry parameters as contact angle, surface tension lowering, solubility, and critical micelle concentration. MATERIALS AND METHODS Normal xanthates from methyl to octyl inclusive and the isopropyl, isobutyl, and isoamyl xanthates used in this investigation were prepared in the usual manner.8 Normal amine hydrochlorides with carbon chain lengths of 1, 2, 4, and 6 were from Distillation Products Industries, of 8 from Archer-Daniels-Midland Co., and of 10, 12, 14 and 16 from Armour and Co. Normal propylamines, pentylamines and heptylamines from Distillation Products Industries were used both as received and as hydrochloride formed by converting the amines according to the procedure described by Li9 Perkin-Elmer Model 521 and 621 infrared spectro-photometers were used to investigate the spectra in the frequency region of 3050 to 2800 cm-' with frequency scale expansion. The accuracy of the frequency readings was within + 1 cm-1. The KBr micropellet technique was used to prepare the xan-thate samples for measurements, and the halocarbon mull technique was used for amines and amine hydrochlorides. EXPERIMENTAL RESULTS Fig. 1 shows the CH3 asymmetric stretching vibrations as a function of the number of carbons in the alkyl group for normal xanthates, isoxanthates and amines. Also included in the figure are data for normal alcohols and isoalcohols taken from the article

Jan 1, 1970

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By A. Tonejc, A. Bonefacic

As can be seen from the phase diagram A1-W1 the equilibrium solubility of tungsten in aluminum is practically nil at room temperature. By quenching from the liquid state (50,000°C per sec), Varic, Burov, and Kolesnicenko2 obtained A1-W solid solutions up to 0.15 at. pct W. The quenched alloys were in the form of foils, 0.2 to 0.3 mm thick. Considering the results of Duwez and Willens,3 it is obvious that this thickness, which makes impossible a sufficiently rapid quenching, was the main reason for the relatively low content of tungsten dissolved in aluminum found by varic.2 he present note shows that the metastable solubility of tungsten in aluminum can be appreciably extended in aluminum-rich A1-W alloys. The quenching technique and the procedure employed for the preparation of the alloys have been described previously.475 The resulting quenched flakes varied in thickness from 1 to 20 µm from experiment to experiment. However, the measurements of the lattice parameters were carried out only with flakes thinner than 5 µm. The areas of quenched flakes were between 0.1 and 15 mm2. The quenched flakes were placed into a 0.3-mm glass capillary tube which was then mounted in a 114.6-mm-diam Debye-Scherrer camera. Straumanis asymmetric film position and nickel-filtered CuKa radiation were used. The lattice spacings were computed taking X(CuKa1) = 1.54050A for resolved and ?(CuKa) = 1.54178A for unresolved doublets. All specimens were rotated at room temperature, 26o +2°C. The lattice parameters were estimated from extrapolation against the Nelson-Riley function. It was estimated that the error in the lattice parameter of the measurements on a single film lies within +0.0004A for lower and about +0.001A for higher concentrations of tungsten. The lattice parameters of the metastable solid solutions A1-W are plotted vs the concentration of tungsten in Fig. 1 together with the parameters measured by previous investigators.' Each point of the present measurements represents a determination of the lattice spacing on different quenched flakes, for a given concentration of tungsten. With experimental accuracy, the lattice parameters of the metastable solid solutions fall on the straight line passing through the already known data.' As estimated from the uncertainties in the lattice spacings of the solid solutions, the alloys were homogeneous within 0.1 at. pct W. The solubility of tungsten in aluminum-rich A1-W solid solutions obtained by a very rapid quenching technique is increased to about 0.95 at. pct W. This value is 6 times greater than the amount known up to now. -he lattice parameters of the resultant aluminum solid solutions with higher concentrations of tungsten than 0.95 at. pct W did not remain constant AUGER electron spectroscopy has been used to clarify the role of impurities in the embrittlement of AISI 3340 steel. Analysis of fracture surfaces has shown that the embrittled condition is correlated with appreciable antimony segregation at grain boundaries. The low temperature (400" to 600°C) temper embrittlement of low alloy steels containing various combinations of Cr , Ni , Sb , Mn , P , Sn , and As has been examined extensively for many years. General reviews of the area have been made by McMahon1 in 1968, LOW' in 1959, woodfine3 in 1953, and Holloman4 in 1946. Recent work by Low, Stein, Turkalo, and LaForce5 has done much in separating the alloy and

Jan 1, 1970

By Yves Dardel

INTRODUCTION SINCE the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts,2 then Baukloh and Oesterlen,3 during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreau,4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per 100 g of metal. Winterhager,5 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitz6 as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhauser8 extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per 100 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per 100 g, while that of the usual apparatus was only about 0.2 cm3 per 100 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. [ ] Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of Eborall and Ransley, as well as the earlier apparatus,

Jan 1, 1948

By P. W. Neurath, R. E. Waite

INFORMATION is available on the effect of stress on permeability, coercive force, and hysteresis for a variety of materials&apos; but for the technically important grain-oriented 3 pct Si-Fe&apos; the stress effects are not adequately covered in the literature; in addition, most of the stress data do not permit estimation of what would happen to the 60 cycle watt losses of the material under stress. Direct measurement of these effects therefore has been made and appears to be of considerable theoretical as well as practical interest. Losses were measured on the central 25 cm portion of 40~3~0.035 cm samples which could be stressed in a small tensile machine built for this purpose. Under tension the following effects, illustrated in the figures by a particular example, were observed: 1—"Unstrained" material of commercially acceptable loss level shows no change or a small increase in loss at low elastic stresses. For the sample shown in the figures, this is illustrated during the initial run, where a 7 pct increase is observed (Fig. 1). 2—There is no additional change in loss when the sample is further strained up to the elastic limit (Fig. 1). Within that limit the loss-stress curve is reversible. This is not illustrated in Fig. 1. 3—Even in the plastic range only small increases in loss are observed as long as the sample is kept under stress (Fig. 2, point N); often no increase can be observed (Fig. 1). 4—A large increase in watt losses is observed after removal of the stress subsequent to plastic deformation (Figs. 1 and 2). 5—All, or nearly all, of the foregoing increase in loss due to plastic deformation can be eliminated by a reapplication of tensile stress but returns upon removal of this stress. This is illustrated in the third run (Fig. 3). This run remains within the elastic limit and shows the reversibility of the stress-loss curve under this condition. These findings have been confirmed on large Samples (approximately 200~10~0.035 cm and larger) except that under 1 no initial increase in loss was ever observed on these. The accuracy of the watt loss measurements is of the order of 1 pct. Neither bending of the sample in the tensioning device nor a redistribution of flux along the width of the sample accounts for these results. They therefore must be explained on the basis of either a change in the domain configuration due to stress or a change in the domain wall mobility. Acknowledgment The assistance of Mr. Robert L. TenBroeck with the instrumentation is gratefully acknowledged.

Jan 1, 1956

By Geoffrey Gilbert

The Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since 1930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. History The occurrence of rock phosphate in Montana has been known since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913. In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Con-solidated&apos;s phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 3/4 miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. Geology The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1948

By Geoffrey Gilbert

The Montana Phosphate Products Co., subsidiary of the Consolidated Mining and Smelting Company of Canada, operates three phosphate properties north and northeast of Garrison, Powell County, Mont. Production of all three is from the same phosphate bed, a 3 to 4-ft. member of the Phosphoria formation, whose outcrop is traceable across the mountains of the Garnet Range in a series of southeasterly pitching folds. Because of topographical differences and of variations in the attitude of the bed, each property has its own mining methods and problems. Most of the phosphate rock produced since 1930 has been shipped to the plant of the Consolidated Mining and Smelting Co. at Trail, B.C., where it is treated with sulphuric acid for conversion to phosphoric acid, which in turn is used to produce various fertilizers. History The occurrence of rock phosphate in Montana has been known since 1910, and the Garrison area was mapped by the United States Geological Survey in 1913. In the nineteen twenties William Anderson, owner of a ranch 8 miles north of Garrison, discovered phosphate on his land, and the Montana Phosphate Co., which later became the Montana Phosphate Products Co., was formed to work the deposit. Montana Phosphate Products Co. later obtained United States leases on two adjoining parcels of ground, and this combined property, known as the Anderson mine, has been the main source of Con-solidated&apos;s phosphate rock. The mine now includes an adjoining parcel leased from Anaconda and mined from the Anderson workings. In 1940, the Graveley mine, a small privately owned property 6 miles east of the Anderson, was leased from the owner by Montana Phosphate Products Co., and a U. S. lease held by Graveley on some adjoining ground was subleased. In 1943 the Luke mine, on the Mineral Hill property, 1 3/4 miles south-southwest of the Graveley, a U. S. lease, which previously had produced a few thousand tons, was optioned from the lessees by Montana Phosphate Products Co., and is now being developed. At both these mines the rock is appreciably higher grade than at the Anderson mine. Geology The Phosphoria formation is the Permian member of an extensive sequence of Paleozoic and Mesozoic rocks. It is underlain by Pennsylvanian (Quadrant) quartzite and Mississippian limestone, and overlain without any marked unconformity by Jurassic (Ellis) shale and Cretaceous shale and sandstone. In the Garrison area, the Phosphoria itself consists mainly of about 50 ft. of gray to yellow chert. Immediately below the chert is the phosphate, usually 3 to 4 ft. thick. Below the phosphate occur a few

Jan 1, 1948

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.&apos;-4 Samsonov et al.&apos; reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami&apos;s Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965

By S. Yukawa, M. J. Sinnott

A high resolution autoradiographic study of the diffusion of a nickel isotope (NP3) into copper in the temperature range of 650° to 925°C, with particular emphasis on grain boundary diffusion, has been made. The extent of grain boundary diffusion is a function of the grain boundary angle and the diffusion temperature. The ratios of the grain boundary diffusion coefficient to the lattice diffusion coefficient ranges from 104 to 105. The activation energy for grain boundary diffusion decreases with increasing grain boundary angle. STUDIES and reviews&apos;-8 of metallic diffusion have indicated that grain boundary diffusion is a common phenomenon but quantitative studies of the many variables involved are not numerous. The present work was concerned with determining the influence of the crystallographic orientation of the grain boundaries and the temperature on the extent of boundary diffusion of nickel into copper. The study involved essentially three steps: 1—the production of grain boundaries of known crystallographic orientation, 2—the determination of the extent of diffusion into the boundaries, and 3—the analysis of the resulting data in terms of the usual diffusion concepts. The grain boundaries investigated approximated the simple tilt variety having l° of freedom. They were produced by controlling the solidification from a melt of Cuprovac (a high purity vacuum-melted copper obtained from Vacuum Metals Corp.) of a pair of seed crystals so that the bicrystals of copper produced had a common <100> axis. By rotating one seed crystal relative to the other, a simple tilt boundary was produced. The angle of rotation between the two crystals is the grain boundary angle 8, or what is sometimes termed the misfit angle. In all, some 16 boundaries ranging from 2" to 72" in 5" to 10" steps were investigated. The crystallographic orientations were measured with the use of both X-ray and optical goniometric techniques. The <100> axes in the crystals were found to be parallel within 2" to 3" with the exception of one crystal (8 = 12") in which the axes were 6" from being parallel. All bicrystals showed evidences of sub-grain structures. Laue analyses showed that these subgrains differed in orientation up to a maximum of 2". Because of these variations, and some curvature in the boundaries, the grain boundary angles listed are actually average values and deviate from the 1 o of freedom boundaries. The stripping film technique of high resolution autoradiography was used to detect the diffusion of the nickel isotope into the grain boundaries of the bicrystals of copper. Kodak experimental permeable stripping film with an emulsion layer 5 u thick

Jan 1, 1956

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE large difference in the X-ray scattering factors for molybdenum and manganese makes the o- phase in the Mn-Mo system an interesting one to study with respect to ordering of the atoms. Such a study has been carried out using data obtained from a powder sample, and the resulting evidence for ordering in this compound is presented here. It is not possible, of course, to obtain all the details of structure for a u phase from powder data only. Most difficult of all would be the determination of precise atomic parameters. There is reason to believe, however, that the atomic parameters do not vary greatly in the different s&apos;S and that the precise values obtained from one s structure would then allow decisions as to the ordering of atoms to be made when there is a large difference in scattering factors. In particular, the powder intensities for Mn-Mo s are for the most part in good agreement with those observed for Co-Cr, for which single crystal studies have been made by the authors.&apos; There are a few marked discrepancies in the intensity comparison of the two s&apos;s, and these cannot be removed by adjustment of the parameters. They are interpreted as resulting from a more pronounced effect of ordering of the atoms. Accordingly, the parameters of Co-Cr s&apos; have been used for the calculations of the Mn-Mo intensities. For Co-Cr, the space group is D4h14-P4/mnm with atoms in the following positions: 1—2 in (b); 11—4 in (f), with x=0.1031; 111—8 in (i), with x= 0.3713 and y=0.0370; IV—8 in (i), with x=0.5662 and y=0.2396; and V—8 in (j), with x=0.3160Y and y — -0.250. The unit cell is tetragonal, with an==9.10A and cn=4.74A for the Mn-Mo u phase studied here.

Jan 1, 1955

By R. P. Carreker

GERMANIUM is a member of that group of ele-nents—carbon, silicon, germanium, and tin-— that are currently of particular interest because of their interesting electrical properties. Near room temperature these materials of diamond cubic crystal structure are characteristically brittle. However, there have been several recent reports that germanium is not brittle at elevated temperatures These observations may be summarized as follows: 1—Germanium single crystals were observed to creep in bending under a maximum fiber stress of 6 kg per mm&apos; (8500 psi) at 500°C and above.&apos; The creep curves were sigmoidal, with an induction period that decreased with increasing temperature. 2—Germanium crystal bars have been bent 90" about radii ten times the bar thickness at 550°C.&apos; 3—-Audible clicks were heard when l/4 in. thick crystals were bent drastically at 450" to 500°C. No microstructural evidence of mechanical twinning was observed 4—Slip lines have been observed in tensile specimens deformed at 600°C, and are coincident with (111) planes, the close-packed planes of the diamond cubic structure.] The slip direction has not been established. 5—A germanium crystal has been compressed approximately 20 pct along a <110> axis at 700°C." The results reported subsequently were obtained in exploratory experiments intended to indicate some aspects of the behavior of germanium single crystals when tested in simple tension. Specimen Preparation A single crystal bar of n-type germanium was used. It was of purity corresponding to a resistance range of 2 to 20 ohm-cm. Tensile specimens were prepared by cutting small rectangular bars

Jan 1, 1957

By C. E. Birchenall

DaVIES and Richardson1 have measured composition changes for Mn1-Owith variation in the equilibrium partial pressure of oxygen at 1500°, 1575°, and 1650°C, where 6 is the deviation from the simple stoichiometric ratio. No trend in this relationship with temperature was observed, so these remarks apply to the whole temperature range. The experimental values and their spread are shown by the bounded straight-line segments in the figure. Davies and Richardson assume that the stoichiometric oxide shows Frenkel disorder, given by the equation Mn2+Mn2+ + Mn" [1] where Mn2+ is a normal lattice ion which moves into an interstitial site (Mni2+) leaving a vacancy (Mn,"). The superscript dashes indicate that there is an excess charge on the anions surrounding the vacancy. Schottky disorder, in which a perfect crystal acquires equal numbers of cation and anion (Ov") vacancies according to leads to equations of exactly the same form in the analysis below. In view of the neutron diffraction results of Roth,2 which shows extensive Frenkel disorder in Fe1-o, Eq. [I] seems more appropriate. The deviations from stoichiometric composition, MnO, result from the addition of oxygen according to In effect Davies and Richardson ignore the variation of Mn3+in constructing equilibrium constants. This approximation might not appear to be very serious if the excess positive charges are really free posi- tive holes (P+) and if the intrinsic conductivity is high as a result of the reaction where e- is a conducting electron. However, the calculations of Buessem and Butler3 indicate that the partition functions of the free charges make a large contribution to the equilibrium constant, and this approximation would not be a desirable one. Furthermore, Morin4 shows that the positive holes are probably localized in MnO and therefore are described better by the mass action principle than by a degenerate gas model. Davies and Richardson&apos;s considerations require that activity corrections be applied beyond a 6 value of about 0.005. It is proposed to show here that the dissociation pressure curve can be calculated reasonably well over the whole composition range studied without activity corrections by choosing appropriate equilibrium constants for reactions 1 and 2. As stoichiometric composition The mass action constant, Ks, for reaction [I.] and the equilibrium constant, K,, for reaction [2] are given by where the concentrations which do not change significantly have been absorbed into the constants. The brackets denote concentrations. The deviation from stoichometric composition is given by gardless of [Mni2 ]. Substituting Eq. [7] in [6]

Jan 1, 1961

By G. W. Imholz

The effect of new discoveries and development of other pools recently discovered is reflected in the increase in production from 586,000 bbl. during 1940 to 758,000 bbl. during 1941 in Coleman County. The States Oil Company&apos;s No. I Hudson, Coleman County, was the discovery well of the Silver field, with a total depth of 3540 ft.; initial production, 10,000,000 cu. ft. of dry gas and 60 bbl. of oil per day from the Gray sand, topped at 3482 ft. The first well drilled in the new Jim Ned field was the Merry Bros. and Perini No. I Greer, also in Coleman County. It had a total depth of 3937 ft. and an initial production of 152 bbl. of 42" gravity oil in 6 hr., through I-in. choke, from Gray sand encountered from 3909 to 3937 feet. J. E. Farrell&apos;s No. I Rose, Haskell County, was a new discovery, around which no additional wells have been drilled. Total depth was 3002 ft., plugged back to 2780 ft. to test an oil sand encountered from 2663 to 2685 ft., which when perforated with 76 shots at that depth was good for 85 bbl. of 40" gravity oil. In Fisher County, General Crude drilled its No. 12 Flanagan to a total depth of 6746 ft. After plugging back to 4578 ft. to test a sand encountered from 4515 to 4528 ft. it was abandoned as a dry hole. The top of the Ellenburger was reported as 6094 feet. Interest in Jones County continued unabated, largely through the development of the Wimberly pool in the southern part of the county, where five Cisco sands are producing. At present the pool has been defined on the south and the southwest. The structure has 170 ft. of closure; the lower limestone pays producing on top of the structure and the fist pay encountered, the Akard sand, producing on the flanks of the structure. Five deep wells were drilled in Stonewall County (H. and T.C. survey)—the Shell Oil Company&apos;s No. I-A Patterson, in block D, with a total depth of 6827 ft., dry and abandoned; the Shell Oil Company&apos;s No. I Rutherford, block I, with a total depth of 6239 ft., dry and abandoned; the Leader Oil Company&apos;s No. I Bilberry, block D, with a total depth of 5700 ft., dry and abandoned; Forest Development Company&apos;s No. 2 Boyd, block D, with a total depth of 4753 ft., dry and abandoned; and the Hunter et al. No. I Boyd, block D, total depth 4757 ft., dry and abandoned. J. E. Farrell drilled his No. I Tipton south of a well that produced from a Strawn sand for some time, to a total depth of 5202 ft., where it was abandoned. The well is in the southwest corner of sec. 43, block 19, T. and P. survey, Nolan County.

Jan 1, 1942

By G. W. Imholz

The effect of new discoveries and development of other pools recently discovered is reflected in the increase in production from 586,000 bbl. during 1940 to 758,000 bbl. during 1941 in Coleman County. The States Oil Company&apos;s No. I Hudson, Coleman County, was the discovery well of the Silver field, with a total depth of 3540 ft.; initial production, 10,000,000 cu. ft. of dry gas and 60 bbl. of oil per day from the Gray sand, topped at 3482 ft. The first well drilled in the new Jim Ned field was the Merry Bros. and Perini No. I Greer, also in Coleman County. It had a total depth of 3937 ft. and an initial production of 152 bbl. of 42" gravity oil in 6 hr., through I-in. choke, from Gray sand encountered from 3909 to 3937 feet. J. E. Farrell&apos;s No. I Rose, Haskell County, was a new discovery, around which no additional wells have been drilled. Total depth was 3002 ft., plugged back to 2780 ft. to test an oil sand encountered from 2663 to 2685 ft., which when perforated with 76 shots at that depth was good for 85 bbl. of 40" gravity oil. In Fisher County, General Crude drilled its No. 12 Flanagan to a total depth of 6746 ft. After plugging back to 4578 ft. to test a sand encountered from 4515 to 4528 ft. it was abandoned as a dry hole. The top of the Ellenburger was reported as 6094 feet. Interest in Jones County continued unabated, largely through the development of the Wimberly pool in the southern part of the county, where five Cisco sands are producing. At present the pool has been defined on the south and the southwest. The structure has 170 ft. of closure; the lower limestone pays producing on top of the structure and the fist pay encountered, the Akard sand, producing on the flanks of the structure. Five deep wells were drilled in Stonewall County (H. and T.C. survey)—the Shell Oil Company&apos;s No. I-A Patterson, in block D, with a total depth of 6827 ft., dry and abandoned; the Shell Oil Company&apos;s No. I Rutherford, block I, with a total depth of 6239 ft., dry and abandoned; the Leader Oil Company&apos;s No. I Bilberry, block D, with a total depth of 5700 ft., dry and abandoned; Forest Development Company&apos;s No. 2 Boyd, block D, with a total depth of 4753 ft., dry and abandoned; and the Hunter et al. No. I Boyd, block D, total depth 4757 ft., dry and abandoned. J. E. Farrell drilled his No. I Tipton south of a well that produced from a Strawn sand for some time, to a total depth of 5202 ft., where it was abandoned. The well is in the southwest corner of sec. 43, block 19, T. and P. survey, Nolan County.

Jan 1, 1942

By P. K. Koh

With identical annealing heal treatment the development of major annealed texture component seems to depend primarily upon the degree of cold reduction. Cube texture was evident on annealing- 1/2-, 1,/4- , and 1/8-mil tapes at 760°C, but it dissap-)eared on 927°C annealing of 1/8-mil tape cold reduced 96.9 pct. Some cube texturee remained as tile strongest 927 °C annealed texture component in 1/4- and 1/2-mil tapes cold reduced 93.8 and 87.5 pet, respectively. The switching coefficient increases and the squareness ratio of the hysteresis loop decreases proportionally with increasing cube pole concentration. PREVIOUS studies 1,2 on the 1/8-mil ultra-thin molybdenum permalloy tape established cold rolled and annealed textures and their magnetic performance for switch-core and coincident-current memory applications, The major cold-rolled texture was found to be of {110}<335> which is quite similar to the cold-rolled texture of silver and 70-30 cartridge brass. The major annealed texture components were found to be of {120)-- <001> and {113)<785>. Although the direction for easy magnetization for this type of alloy by the single-crystal technique is not avaliable, knowledge from related studies indicated [Ill] as the easy magnetization direction, similar to that of nickel.&apos; Therefore, a cube orientation, if present in the tape core, would be most detrimental to its magnetic performance.3 In its cold-rolled state the tape had < 111 > directions in the rolling plane 14.5 deg from the rolling direction.&apos; But the coercive force of the tape in such condition will be excessive due to large amounts of internal stresses, and therefore makes its use impossible for memory applications due to long switching time. In lower nickel alloys, suchas 50-50 nickel-iron and 65 pct Ni-Fe sheets, previous investigators4"7 found the presence of cube texture on annealing at 900° to 1000°C. Although no cube texture was found in annealed 1/8-mil tape,"&apos; its presence in some annealed 1,/4-mil tape cores was firmly established a year ago as verified by significant differences in magnetic properties. The present investigation is devoted to the orientation study and related magnetic measurements on three thicknesses of the ultra-thin tape, namely, 1/8 mil, 1/4 mil, and 1/2 mil, cold rolled directly from annealed 4-mil stock in the cold-rolled state as well as after they were annealed at 760°C (1400° F) and 927°C (1700°F). The results obtained might serve to elucidate the development of annealed texture as well as to establish clearly the importance of preferred orientation on the magnetic performance of such memory tape core despite its well-known low magnetic anisotropy exchange energy. EXPERIMENTAL PROCEDURE Samples were taken from one production heat (0.010 wt pct C, 0.004 P. 0.016 S, 0.80 Mn. 0.29 Si. 79.69 Ni. 4.42 Mo. 0.054 Co, 0.002 Ti, 0.12 Al, 0.04 Mg, 14.56 Fe). Annealed 4-mil sheets were cold re-

Jan 1, 1962

By Jim Douglas, H. H. Rachford, D. W. Peaceman

The problem of unsteady-state gas flow through porous media has been solved numerically only for the case of linear or radially symmetric reservoirs. A recently introduced numerical method for solving the unsteady-state heat flow equation in two dimensions is applied to the calculation of the depletion of a square region containing a perfect gas. Solutions are presented in graphical form for various values of dimensionless parameters. The solutions are compared with published .solutions for radial reservoirs. I NTR ODUCTION The problem of unsteady-state flow of gas through porous media gives rise to a second-order non-linear partial differential equation for which no analytical solution has been found. Numerical approximations to solutions of the gas flow problem have been obtained by the stepwise solution of an associated difference equation1,2. However, the methods so far developed have required that the reservoir be either linear or radially symmetric. This restriction in shape has been necessary so that only two independent variables be considered, namely, one distance variable and time. In order to deal with reservoirs having more realistic shapes, it is necessary to develop numerical procedures for the solution of the gas flow problem involving two distance variables. A numerical procedure, denoted as the alternating-direction implicit method, for the solution of the heat-flow problem in two dimensions has recently been introduced" By the use of this procedure, approximate solutions have been obtained for heat-flow problems in a square8, and in regions having various non-rectangular boundariesa. Because of the similarity between the equation for heat conduction in solids and the equation for gas flow in porous media, it is reasonable to expect that the alternating-direction implicit method should also be useful for solving the gas flow problem in various two-dimensional regions. Solutions have been calculated for the simplest two-dimensional region, a square reservoir with a single well in the center. While reservoirs of such simple geometry seldom, if ever, exist, the solution of this problem is of some practical importance because it is also the solution of another problem, that of determining the depletion history about an individual well in an infinite uniform reservoir containing wells spaced throughout on a square lattice and producing equally from each well. Finally, it is of interest to compare solutions for a square reservoir with those for a circular reservoir and to determine the effect of the shape of the boundary for that particular case. METHOD OF CALCULATION Basic Differential Equation By combining the equation of continuity, the perfect gas law,

Jan 1, 1956

By R. G. Davies, R. H. Richman

Several techniques, X-ray diffraction, transmission electron microscopy, conventional, metallography, and mechanical property measurements are combined to investigate decomposition in the suPersaturated solid solution Fe-27 at. pct Be. The following sequence of structures for aging temperatures below 400°C is established: massive short-range order, pseudo-FeBe (L2o) order, Fe3Be (DU3) order, sinusoidal modulation of composition, general or continuous precipitation, and discontinuous or cellular precipitation. In addition to this sequence itself, several features of the individual stages are noteworthy; for example, when coherent modulations occur, their development is parallel to (100) everywhere in the specimen apparently without incubation, and both the wavelength and the composition amplitude of the modulations increase with aging time. Two types of discontinuous reaction are observed, depending upon the aging temperature. At low temperatures (<550°C) the boundary-nucleated variety of discontinuous precipitate predominates; but at higher temperatures (>600°C) the crystallographic variety occurs instead. Hardness and flow-stress measurements clearly reflect the quoted structure sequence. Some qualitative aspects of the structure changes and of the relationship between mechanical properties and structure are discussed. BERYLLIUM in solid solution markedly strengthens iron.&apos;" A recent study demonstrated that not only were supersaturated single crystals of Fe-27 at. pct Be very strong, but they deformed primarily by mechanical twinning.3 Such behavior, coupled with the decrease in solid solubility of beryllium in a Fe from about 33 at. pct at 1165°C to about 10 at. pct at 500°C4 as shown in Fig. 1, leads naturally to questions about property changes with aging in this system. In 1929 roll,1 and later Seljesater and Rogers,5 reported that useful increases in strength could be obtained by aging quenched Fe-Be alloys, but it was not until quite recently that any of the details of precipitation in these alloys were studied. Richman6 observed that both an Fe3Be superlattice (with a DO3 crystal structure the same as Fe3A1, illustrated in Fig. 2) and a modulated structure preceded the appearance of a discrete second phase in the 20 at. pct Be composition. Here, a modulated structure refers to a periodic composition fluctuation within one crystal, while its lattice remains coherent. Subsequent work on a Fe-Be alloys by Heubner7 and von Heimendahl and Heubner8 confirmed the existence of the modulated structure, although only an FeBe (L20) ordered structure was detected (also shown in Fig. 2). Both Rich-man and Heubner corroborated the large increases in hardness during aging reported earlier, but other mechanical properties were not examined. Since modulated systems are encountered relatively infrequently, the influence of coherent modulation upon mechanical properties is not well-known. With the accumulation of information about age-hardening systems, it has become clear that many precipitation reactions cannot always be described by the concept of heterogeneous nucleation at some lattice discontinuity followed by diffusional growth. Rather, complex sequences involving prior "preparation" of the matrix are quite common; that is, a transition structure occurs in the parent phase, instead of in some "nucleus" form. Delineation of such subtle sequences appears to be a worthwhile step toward the understanding of solid-state precipitation. Since not many structural progressions of comparable nature have been reported, the objectives of the present survey are to identify and elucidate the various

Jan 1, 1967