Search Documents

By Albert D. Brokaw

THE accompanying chart was devised to provide a rapid and simple method of correcting for temperature and compressibility (deviation from Boyle's law) of gas under relatively high pressures and temperatures, such as are encountered in many deep reservoirs. The chart was prepared by interpolating for the desired values in the experimental data of Burke and Keyes1 and Kvalnes and Gaddy2 on the compressibility of methane, after adjusting their results from 0°C. to 60°F. and combining the correction factors for compressibility and temperature into a single multiplier, which, applied to the product of pressure and reservoir volume, gives at once the volume at one atmosphere (14.7 lb. per sq. in. abs.) and 60°F. The relationship 0f this multiplier to the compressibility factor Z, as used in most discussions, is simply: [Multiplier = 460° + 60°ZT –] where Z is the compressibility factor and T the absolute temperature (Rankine). Fahrenheit temperatures are shown on the vertical axis and pressures in pounds per square inch absolute on the horizontal axis. Correction factors or multipliers at intervals of 0.05 from 0.55 to 1.40 have been plotted on the chart and are calculated t0 give volume of gas at one atmosphere pressure (14.7 lb.) and 60°F. The operation is as follows: The reservoir volume, times the number of atmospheres pressure, times the multiplier, gives the volume of gas measured at one atmosphere (14.7 lb. per sq. in.) and 60°F. For example, a reservoir is estimated to have a volume of 10,000,000 cu. ft., bottom-hole pressure is 2940 lb. per sq. in. and temperature is 184°F To make the correction for methane, follow the 184° line horizontally to the 2940-lb. pressure line. The intersection lies between the 0.85 and 0.90 correction lines, and by interpolation we may estimate the multiplier at 0.863. The computation is simply: [ ] Using the chart for methane prepared by Prof. G. G. Brown3 and his associates, the multiplier is found to be 0.867. Details 0f computation are as follows: Correction factor to apply to PV to correct for deviation from Boyle's law and adjust to measurement basis of 60°F.: [ ]

Jan 1, 1941

William Kelly, Vulcan, Mich.:—In the northern part of Bedford county, Pa., the county immediately south of Huntingdon, the Clinton measures appear along the eastern slope of Tussey mountain near its base. The only iron-ore bed that has been worked is in the upper part of the formation. Along the mountain this seam has a dip of more than 60°. At the outcrop the ore is soft and rich, but with depth it passes often abruptly into an almost pure limestone similar to that described by Dr. Rutledge. The soft ore extends deeper in the cross-gullies than it does under the higher gound between the depressions. The slates adjoining the rich ore have been weathered, but where in juxtaposition to lean ore and limestone they are hard. The alteration of the ore-bed is evidently the result of the conditions of drainage in quite recent geo-

Jan 1, 1910

By B. Post, D. Moskowitz, F. W. Glaser

Lattice parameters of various hafnium compounds, two borides, a carbide and a nitride were determined. Some physical properties were measured and comparisons with the properties of the corre-sponing zirconium compounds were drawn. A LTHOUGH borides of transition metals have A been extensively investigated in recent years, there are few references in the literature to borides of hafnium. This is not surprising, in view of the extreme scarcity and great cost of the purified metal. Becker' reported the existence of a boride, carbide, and nitride of hafnium; he listed the formulas as HfB, HfC, and HfN. However, in his work no mention was made of chemical analyses of the reaction products. In this paper results of a study of various hafnium compounds, including borides, carbides, and nitrides, are reported. It was expected, of course, that these compounds would closely resemble their zirconium analogues, which have previously been extensively investigated. Three borides of zirconium are known: ZrB,² ZrB,² and ZrB212.4 In addition, one carbide, ZrC,5 and one nitride, ZrN,5 have been reported. It should be noted that ZrB and ZrB12 are stable phases only in relatively high-temperature regions, unlike ZrB2, which is stable from room temperature to its melting point." It was felt that hafnium would yield corresponding borides, carbides, and nitrides with similar stability ranges. Experimental Procedures and Results A quantity of hafnium metal that was better than 97 pct pure, with zirconium as its major impurity, was furnished by the Argonne National Laboratories. The boron powder used was approximately 96.5 pct pure. In general, the procedure involved mixing the metal and boron powders in the desired proportions, and subsequently hot pressing them. The resulting specimens were analyzed chemically and phases present were identified by X-ray diffraction methods. A Philips Norelco Geiger counter spectrometer was used for identification of components and for measurement of lattice constants. Filtered copper radiation was used for all X-ray work. Electrical resistivity and density measurements were carried out at room temperature. The stable diboride, HfB2, will be described first. Stoichiometric quantities of boron and metal were heated to approximately 2000°C during hot pressing. The reaction product was shown by X-ray diffraction methods to be isomorphous with ZrB2 (space group Dlgh; P6/mm). Values of lattice constants of HfB2 compared with those of ZrB2 are shown in Table I. The calculated density of HfB2 is 11.2 g per cc, compared with a measured (pycnometric) value of 10.5 g per cc. HfB2 specimens prepared under a wide variety of conditions (including variations in initial Hf-B ratios) showed only insignificant variations in lattice constants, indicating a very narrow range of homogeneity. Like ZrB2,7 HfB2 is an excellent electrical conductor. The resistivity at room temperature of hot-pressed samples, approximately 85 pct dense, is 12 microhm-cm. This compares favorably with the electrical resistivity of 10 mi-

Jan 1, 1954

By R. R. Goddard

By use of the frequency response method with a radioactive tracer, it was possible to determine fluid dispersion and distribution in a natural consolidated and an unconsolidated medium. Measurements were made in a linear flow system at oleic saturations of 69 per cent in the consolidated medium, and 100 per cent in both media. Dispersion and distribution were obtained by measuring the amplitude attenuation and the phase velocity of sinusoidal waves with a dual monitor apparatus. The gamma ray emissions permitted in situ measurements at any distance along the porous samples. One result of importance was that the effective diffusivity increased as the wave length increased. As a consequence, a dispersion coefficient appropriate for the injection of large slugs might exceed the value measured by use of small slugs. Since flow models based solely on fluid velocity and an effective diffusivity coefficient imply that the diffusivity should be independent of frequency, such representations were not adequate for the data of this study. A comparison was made with a capacitance model of porous media with deadend PVs, but even this model was not completely adequate. By using attenuation and phase velocity data, fluid dispersion can be predicted without postulating a differential equation satisfied by the tracer concentration, thereby eliminating the need of a complicated model to represent dispersion. INTRODUCTION The flow of similar miscible fluids through a porous medium can be fairly adequately described by two parameters: the average fluid velocity and the effective diffusivity.1-3 It has been pointed out recently, however, that significant discrepancies exist between this representation and the experimental data.4-7 An improved agreement can be obtained by introducing additional parameters based on the concept of dead-end pores. The purpose of the present investigation was to find out whether the frequency response method could be used to measure the relevant parameters. The method was used in the following form. A stream of fluid was flowed at a constant rate through a sample of porous material and the concentration of a radioactive tracer in the fluid was varied sinusoidally at a fixed frequency. The effects of flow through a porous medium are a decrease in the amplitude of the concentration wave and an increase in the velocity of the peaks of the waves above the average velocity. Attenuation and phase veIocity of the waves were measured as a function of frequency and fluid velocity. The simple two-parameter model implies that the diffusivity should be independent of frequency. Data reported in this paper show that the diffusivity decreases as the frequency increases. Hence, as shown also by many others, the two-parameter model is not completely adequate. Coats and Smith 5 used two additional parameters in their model: the volume of the dead-end pores and the rate of mass transfer between dead-end pores and the flowing stream. Their capacitance model of a porous medium containing some stagnant fluid, to which transfer occurs by molecular diffusion, did not explain the dispersion results of either the present study or of theirs. Instead, the capacitance effect can be better described as the result of extreme velocity variations within the pores of the medium, with transfer between the velocity zones by convection. EXPERIMENTAL PREPARATION OF POROUS MEDIA Data reported here were obtained with a natural Berea sandstone, and with two packings of 20/25 mesh sand. Pertinent information about these media is listed in Table 1. The sandstone core was first sealed with a non-

Jan 1, 1967

By D. M. McFarland

A FEW years ago a novel electric detonator known as the split-second or millisecond delay electric blasting cap was introduced for use in quarry blasting. Regular electric blasting caps fired in series may be depended upon to fire within a millisecond or so from the first to the last in a series. Regular delay electric blasting caps are provided that fire one period after the other period in intervals of 1/2 to possibly 1 1/2 sec. Most split-second or millisecond delays are designed to fire one period after the other period in possibly 25 to 50 millisecond intervals. The ear is not capable of detecting time intervals of this magnitude. The primary thought at the time millisecond de- lays were introduced was to investigate the results on rock breakage by firing a line of holes in a quarry face.so that charges in adjacent holes would not be detonated simultaneously. This could not be accomplished satisfactorily with regular delays. The time interval between successive periods of $5 to 1 sec was sufficient to permit considerable movement of the burden. If the burden of one hole was reduced to a great extent by the firing of an adjacent hole, the firing of the hole with the reduced burden would likely reveal this lack of confinement by a terrific report and wild throw of rock.

Jan 1, 1950

By R. H. Sweetser

AT the Buffalo meeting in October, 1898 (Trans., xxviii., 865), our Secretary, Dr. Raymond, in speaking of the obstacles he had encountered in securing contributions to the Transactions from members in practice, said: "It is the disinclination of many members to communicate incomplete or partial or preliminary results. They are going to write, ' some day,' a thorough and monumental paper; and meanwhile they prefer to communicate nothing. . . . It is the difficulty to which I have just referred that I have encountered in a wide correspondence with members, undertaken for the purpose of securing contributions of fact and opinion concerning the special subject of this discussion. . . . Almost none of them seem to recognize the value of preliminary, incomplete and indecisive reports of practice, as laying the foundation for a thorough inquiry." This remark was made in immediate reference to a discussion concerning blast-furnace tuyeres ; but, notwithstanding this appeal from the Secretary, little has been recorded regarding the distribution, the penetration, and the pressure of the blast at the tuyeres and inside the iron blast-furnace. I am therefore encouraged to contribute the following incomplete and crude observations of the blast-pressure inside the hearth. At the suggestion of J. H. Frantz, the General Manager of the Columbus Iron & Steel Co., a test was made at the East furnace of the company to determine whether there was any difference in blast-pressure at the different tuyeres. The apparatus used for this test was not sensitive enough to give accurate results. It consisted of a small pressure-gauge mounted on a 3/8-in. gas-pipe. A hollow plug, fitting into the peep-hole of the tuyere-cap, prevented the blast from blowing-out during the test. The test-pipe was held in place by means of the handle on the outer end.

Mar 1, 1909

By C. W. A. Muir

Laboratory and plant-scale testwork on the extraction of gold from highly refractory antimonial and arsenical concentrates using both direct low-alkalinity pressure cyanidation, and acidic pressure pre-leaching followed by ambient low-alkalinity cyanidation, is described. A novel method for treating effluent solutions containing extremely high concentrations of base metal cyanides, as well as arsenic and antimony compounds, was developed in order to make the process ecologically acceptable.

Jan 1, 1984

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

P. L. Pratt (University of Birmingham, Birmingham, England)—The author has measured the hardening effect of isolated edge and screw dislocation boundaries in a remarkably elegant manner, and he proposes that the detailed structure of the boundary determines its effectiveness as a barrier to slip although "there are still unknown details of the distribution which may be extremely important." On p. 678 the author states "that for a good crystal (one having a yield of about 30 psi) a change in annealing temperature from 300" to 400 °C resulted in a negligible shift in the level of the stress-strain curve." Is this in agreement with the results of the earlier paper by Li, Washburn, and Parker8 in which such a change of temperature produced notable hardening in crystals with a yield of about 30 psi? Or were these earlier crystals, of the same nominal purity, less perfect than those used in this work? The experiment illustrated in Fig. 15, p. 681, shows that the boundary has sharpened after annealing at 400 °C, the temperature at which the hardening effect first becomes apparent. Did the author verify that no sharpening of the boundary occurred at, say, 300 °C where no hardening was found? This would seem to be an important check on the proposed mechanism, especially since zinc of this purity should polygonize at temperatures well below 400 °C within the annealing times used here. There seem to be at least two alternative explanations which could fit these facts: 1—The boundary may sharpen at 300 °C or even lower temperatures but be unable to contribute greatly to the hardening until jogged by thermal vacancies and other impurity atoms after 400 °C anneal. This mechan- ism, discussed in the earlier paper,' is believed to account for the thermal hardening observed by Blank'" in NaCl, as stated elsewhere: and by results from recent experiments which tend to confirm this view. 2—The dislocations in the diffuse boundary may be locked by impurity atoms at 300 °C and thus only sharpen the boundary at 400 °C with the aid of thermal vacancies. In this case it would be difficult to distinguish between the two sources of hardening (sharpening or jogging), using metal of this purity. Jack Washburn (author's reply)—The author wishes to thank Dr. Pratt for his discussion. In connection with his first comment, it should be pointed out that the temperature of testing in the present series of experiments was —196°C, whereas, in the earlier experiments he referred to,' it was 20°C. Therefore, the yield values should not be directly compared. It is likely that the crystals used in the present work were initially more perfect macroscopically than the large shear specimens used previously. The small size of the test section in the kink specimens made it possible to select regions of the large crystals, from which they were acid-cut, that were free of observable small angle boundaries. The sharpening of a microscopically diffuse boundary such as that in Fig. 15 begins in zinc of this purity well below 300°C. However, it is probably not justified to conclude that because a boundary looks sharp under the microscope it has attained the ideal structure. The author agrees with Dr. Pratt that jogging of dislocation lines is one of the structural features of a small angle boundary that should be important in determining its strengthening effect. More detailed information concerning the changes in boundary structure as a

Jan 1, 1956

By Charles M. Ryder

IN presenting this paper to the Institute I beg to mention, first, the results which I have obtained and the apparatus which I have employed, and to follow this with a brief description of the steps by which I have perfected this process. My present mode of testing is as follows : I obtain, either from the furnace or from the finished product in any stage in which it may chance to be, a small test-piece, usually about 4 of an inch square by 3 1/2 inches in length. I place this test-piece upon the poles of an ordinary electro-magnet, for about one minute, and thus magnetize it to its extreme limit. I then place it upon an indicator (which I will shortly describe), on which indicator there is already placed a piece of steel of similar form which has been magnetized in the same manner, the percentage of carbon of this second piece being definitely known. I then, by means of a scale, which forms part of the indicator, marked in degrees of carbonization, read the exact percentage of carbon contained in the piece under examination. My apparatus consists of an ordinary electro-magnet, connected with a suitable battery of moderate power, by which I magnetize the pieces as before described, and of an indicator which consists of a magnetic needle suitably mounted or suspended, so that it is free to deviate a few degrees only from the zero point, and having a rest, which is used to check the vibrations when in use, and to support its weight when not in use. At a right angle to the natural position of the needle I have a scale about 3 feet long, the zero point of which coincides with the natural position of the needle. This scale is marked in each direction from the zero point in degrees of carbonization. The marking of the scale is in accordance with the following rule: Taking the carbonization of the steel as a basis, I maintain the same proportion between the squares of the distances on the scale as exists between the percentages of carbon in the steel, for instance, if .08 of

Jan 1, 1877

By S. J. Sindeband

Prior to discussing the metallurgy of sintered chromium borides, it is pertinent to outline some of the reasoning behind this investigation and the purposes underlying the work. This study was initiated as an aproach to the ubiquitous problem of a material for service at high temperatures under oxidizing atmospheres, and it was undertaken with a view to raising the 1500°F (816°C) ceiling to 2000°F (1093°C) or better. For the reason that no small, but rather a major, lifting of the high temperature working limit was being attempted, it was felt appropriate that a completely new approach be taken to this problem. A summary of the thinking behind this approach was published recently by Schwarzkopf.' In briefest terms, it was postulated that the following requirements could be set up for a material which would have high strength at high temperatures. 1. The individual crystals of the material must exhibit high strength interatomic bonds. This automatically leads to consideration of highly refractory materials, since their high energy requirements for melting are related to the strength of their atom-to-atom bonds. 2. On the polycrystalline basis, high boundary strength, superimposed on the above consideration, would also be a necessity. Since this implies control of boundary conditions, the powder metallurgy approach would hold considerable promise. Such materials actually had been fabricated for a number of years, and the cemented carbide is the best example of these. Here a highly refractory crystal was carefully bonded and resulted in a material of extremely high strength. That this strength was maintained at high temperature is exhibited by the ability of the cemented carbide tool to hold an edge for extended periods of heavy service. Nowick and Machlin2,3 have analytically approached the problem of creep and stress-rupture properties at high temperature and developed procedures whereby these properties can be approximately predicted from the room temperature physical constants of a material. The most important single constant in the provision of high temperature strength and creep resistance is shown to be the Modulus of Rigidity. On this basis, they proposed that a fertile field for investigation would be that of materials similar to cemented carbides, which have Moduli of Rigidity that are among the highest recorded. The cemented carbide, however, does not have good corrosion resistance in oxidizing atmospheres and without protection could not be used in gas turbines and similar pieces of equipment. It would be necessary then to attempt the fabrication of an allied material based upon a hard crystal which had good corrosion resistance as well. It was upon these premises that the subject study was undertaken and at an early stage it was sponsored by the U.S. Navy, Office of Naval Research. Since then, it has been carried on under contract with this agency. Chromium boride provided a logical starting point for such research, since it was relatively hard, exhibited good corrosion resistance, and, in addition, was commercially available, since it had found application in hard-surfacing alloys with iron and nickel. That chromium boride did not provide a material that met the ultimate aim of the study results from factors which are subsequently discussed. This, however, does not detract from the basis on which the study was conceived, nor from the value of reporting the results which follow. Chromium Boride While work on chromium boride proper dates back to Moissan,4 there has been a dearth of literature on borides since 1906. Subsequent to Moissan, principal investigators of chromium boride were Tucker and Moody,5 Wede-kind and Fetzer,6 du Jassoneix,7,8,9 and Andrieux." These investigators were generally limited to studies of methods of producing chromium boride and detennining its properties. Some study, however, was devoted to the chromium-boron system by du Jassoneix,7 who did this chemically and metal-lographically. This system is not amenable to normal methods of analysis by virtue of the refractory nature of the alloys involved, and the difficulties of measurement and control of temperature conditions in their range. Dilatometric apparatus is nonexistent for operation at these temperatures. Du Jassoneix made use of apparent chemical differences between two phases observed under the microscope and reported the existence of two definite compounds, namely: Cr3B2 and CrB. These two compounds, he reported, had quite similar chemical characteristics, but were sufficiently different to enable him to separate them. The easiest method for producing chromium boride is apparently the thermite process, first applied by Wede-

Jan 1, 1950

By H. C. Casey, M. B. Panish

The roles of the phase diagram and the diffusion and solubility analyses in the selection of sources for the diffusion of zinc into GaAs are discussed. Isothermal sections of- the phase diagram are described at 1000°, 775°, 744°, and 700°. Below 744° the three solid phases, Zn3As2, GaAs, and ZnAsz, may be in equilibrium. In the composition regions where the three solid phases are in equilibrium, the partial pressures of the components do not vary with composition and there is no liquid phase. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected to yield reproducible diffusion profiles without surface damage. The 5/50/45 ternary source Provides a significant improvement in the reproducibility and planarity of- the zinc diffusion as compared with other zinc diffusion sources that result from starting with elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. Several experimental diffision profiles for the 5/50/45 diffusion source have been determined. The profiles are very steep in the region of the junction and produce devices that exhibit step junction behavior. The junction depth varies as the square root of time. Diffusion at 700°C for 4 hr gives a 5-µ junction depth and a surface concentration of 2.4 x1020 cm-3. The surface concentration is enhanced by a factor of three and the junction depth decreased by a factor of ten as compared with diffusion with a starting source 01- elemental zinc. The differences in dijyusion behavior with these two sources are due primarily to the approximately 10' greater equilibrium As4 partial pressure for the 5/50/45 source. ThE most common technique for the preparation of GaAs p-n junctions for diverse applications ranging from switching diodes to injection lasers has been to diffuse zinc into the solid from the vapor phase. The zinc impurity has generally been provided by introducing into a diffusion ampoule elemental zinc, dilute solutions of zinc in gallium, or various combinations of zinc and arsenic. For the purpose of eliminating surface deterioration, zinc has been diffused into GaAs through SiO2 films1 and from zinc-doped SiO2 films.2 During a study of the injection and recombination mechanisms in GaAs junctions, we found that these diffusion techniques either resulted in nonreproducible diffusion profiles and nonplanar junction interfaces or were extremely inconvenient to use. An unpublished report by Allen and pearson3 emphasized that an understanding of diffusion requires relating the diffusion conditions and system compositions to the ternary phase diagram. Recent studies have made it possible to relate the effect of starting source composition on the GaAs sample surface and diffusion profile reproducibility and, in addition, to estimate the expected surface concentration and zinc diffusivity. These studies include the Ga-As-Zn phase diagram,415 the determination of the incorporation reaction for zinc as a substitutional impurity,6 and the analysis of the concentration dependence of the diffusion coefficient.' In this paper the role of the phase diagram in the selection of the starting diffusion source composition is illustrated, and an application of the diffusion and solubility analyses is used to demonstrate their utility in the estimation of surface concentration and diffusivity for various starting source compositions. Consideration of the isothermal sections of the ternary phase diagram shows that below about 744° C a composition region exists where the three solid phases Zn3As2, GaAs, and ZnAs2 are in equilibrium without a liquid phase. In this region the partial pressures of the components do not vary with composition, and thus the surface concentration and diffusivity depend only on temperature. A diffusion source composition within that region containing 5, 50, and 45 at. pct Ga, As, and Zn was selected. As will be described in detail, this diffusion source yields reproducible diffusion profiles without surface damage, planar junction interfaces, and steep profiles that result in devices with step junction behavior. Only closed diffusion systems are considered. Open or flowing vapor systems require the maintaining of constant vapor pressures in the flowing gas and represent control problems outside the scope of this discussion.

Jan 1, 1969

By S. Feuerstein, L. Rice

The effect of low pressures on the flow and fracture behavior of molybdenum is described. For poly crystalline samples, room-temperature tensile tests indicate greater ductility under 10 Torr than under intermediate pressures up to and including atmospheric pressure (760 Torr). In addition, tests conducted at 760 Torr under atmospheres of air, dry nitrogen, and purified argon exhibited no apparent difference in mechanical properties. Critical tests involving baking in situ as well as those involving single-crystal deformation further imply that the ductility effect is a pressure-dependent phenomenon related only to the fracture process. This dependency is discussed in terms of adsorption and diffusion contributions. THE effect of very low pressures on material properties has heretofore been presumed to be important only for substances possessing relatively high vapor pressures at ambient temperatures. Research has therefore been concentrated primarily on organic solids and liquids, and in some instances on metals such as zinc and cadmium. Most vacuum-effect studies' on the mechanical behavior of metals have been performed under conditions of either cyclic loading or creep rupture at elevated temperatures, i.e., over extended time periods. These studies were not restricted to high vapor pressure materials but also encompassed such metals as gold, copper, and nickel. Very little concern, however, was placed upon the importance of a vacuum environment on the mechanical behavior of metals subjected to a simple unidirectional deformation at ambient temperatures. A tension test is generally of short duration as compared to a creep test, and at room temperature vacuum effects if any would be expected to be surface-limited. In early 1963, Kramer and podlaseck2 reported a change in the bulk flow behavior of aluminum single crystals during room-temperature tension tests. The deformations were performed under pressure conditions of 760 to 3.4 X 10-8 Torr and indicated for the first time a vacuum surface effect contributing to the bulk tensile behavior of metal specimens. As a consequence, an experimental program was initiated in this Laboratory to study the effects of ultrahigh-vacuum conditions on the mechanical behavior of metals. The results of a preliminary study on poly-crystalline molybdenum3 revealed, unlike Kramer's observations of changes in the stress-strain behavior, only an increased ductility under ultrahigh vacuum. Flow behaviors were nearly identical for all tests re- gardless of pressure. This paper presents comprehensive results obtained in this area of research. 1) EXPERIMENTAL PROCEDURE Three material categories were used in this study: sintered and are-cast polycrystalline molybdenum of nominal purity 99.93+ pct and single-pass electron-beam zone-refined molybdenum single crystals having a nominal purity level of 99.99+ pct. The interstitial levels (weight percent) as determined by the Materials Testing Laboratories, Division of Magnaflux Corp., were as follows: sintered molybdenum (C— 0.005, H—0.0004, O—0.015, N—0.008); and arc-cast molybdenum (C-0.0038, H-0.0003, O-0.015, N-0.023). Single-crystal molybdenum obtained from Materials Research Corp. had a typical interstitial analysis of C-0.0015, H-0.00007, O—0.00045, and N-0.0001. Tensile specimens having a 5 mm diam by 50.8 mm length were prepared from these materials. An average grain diameter of 0.059 mm was obtained for the sintered specimens following a 4-hr, 1600°C heat treatment. Grain sizes from 0.019 to 0.149 mm were obtained in the arc-cast specimens following heat treatments from 1100° to 1600°C for 1 hr. This series of specimens was used exclusively for the grain-size effect studies. All samples were electrolytically polished in 97 pct sulfuric acid solution prior to testing. Experiments were performed at room temperature in an ion-pumped ultrahigh-vacuum system positioned in an Instron tensile machine, Fig. 1. A constant strain rate of 4.2 x 10-4 sec-1 as derived from crosshead displacement was assumed for the deformations. Starting vacuums ranged from 2 to 0.5 X 10-10 Torr. These pressure measurements were made using corrected values4 of an NRC Redhead gage. Comparative readings were also made against a G.E. triggered dis-

Jan 1, 1967

By F. C. Schrader, Alfred H. Brooks

Last fall (1899) we had the good fortune to be able to spend a few weeks in the new placer gold-mining region of Alaska, which is known as the Nome region. Cape Nome, after which the region has been named, and which forms the southeastern corner of the Nome Mining District, is an unimportant promontory on the southern coast of the Seward Peninsula (see map, Fig. 1). The name Seward has recently been given to the great peninsula which forms the northwestern extremity of Alaska. To the north of it is the Arctic ocean, to the south Bering sea, while its wesbernmost extremity, Cape Prince of Wales, is separated from the Asiatic coast by the Bering straits. The coast line of the peninsula is of a cuspate character, consisting of a succession of sandy, crescent-shaped beaches and rocky headlands. The interior has been but little explored; but we know that it is comparatively rugged, the higher mountain peaks rising probably from 4000 to 5000 feet in elevation. The mountains have an easterly and westerly trend, and the water-shed between the two oceans probably nearly bisects the peninsula. At Golofnin bay, the southeastern part of the Seward peninsula, some spruce is found, but to the west the region is entirely timberless, except for a sparse growth of stunted

Jan 1, 1901

By Raymond B. Ladoo

ABRASIVES include the substances, natural or artificial, that are used to grind, polish, abrade, scour, clean or otherwise remove solid material, usually by rubbing action but also by impact (sandblasting, for example). They do not include abrasive tools-for instance, lathe tools and files-or polishing agents such as waxes, which act by filling pores. Detergents and cleaners whose action is chemical rather than physical are omitted although some chemical action polishes and cleaners may also contain solid abrasives; for example, many metal polishes. GENERAL CONSIDERATIONS The most important physical properties of materials that qualify them for use as abrasives are hardness, toughness (or brittleness), grain shape and size, character of fracture or cleavage, purity or uniformity. For making bonded grain abrasives such as grinding wheels, additional important factors are stability under high heat and bonding characteristics of grain surfaces. The economic factors of cost and availability are always important. No one single property is paramount for any use. For some uses extreme hardness and toughness are needed, as in diamonds for drill bits; for others, the factors of greatest importance are hardness and ability to break down slowly under use, to develop fresh cutting edges when grains become worn-for example, in garnet for sandpaper, neither highly cleavable or friable grains nor extremely tough grains

Jan 1, 1949

By Y. Dardel

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? then Baukloh and Oesterlen,a during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreq4 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 I00 g of metal. Winterhager,6 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 Schweinitze 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, Steinhausers extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per I00 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 I00 g, while that of the usual apparatus was only about 0.2 cm3 per I00 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. Table i—Amount of Adsorbed and Dissolved Hydrogen (After Eborall and Ransley) Extraction Hz Adsorbed „ h2 dissolved Temperature Calculated Extraction OCcma 500 0.057 0.050 600 0.062 o.096 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, 1949

By H. J. Ramey

A general solution is presented for the transient temperature distribution caused by radial movement of a cylindrical heat source through a homogeneous medium of infinite extent. This problem represents a highly simplified model of the movement of a combustion front during the thermal recovery of oil. Numerical solutions are presented for a heat source moving at a constant velocity, and a velocity inversely proportional to the radial location of the heat source. Numerical solutions are presented for both finite and infinite vertical thickness of the heat source, i.e., with and without vertical heat losses. The numerical solutions are used to estimate the fuel concentration needed to maintain a combustion front during the thermal recovery of oil. The sensible heat carried to the combustion front by the injected gas stream is discussed in regard to the fuel concentration. Numerical solutions for a heat source (combustion front) of finite vertical thickness indicate the field conditions that may be necessary to sustain the temperature of a combustion front above the ignition temperature of the fuel over considerable distances from an injection well. The results also have implications in regard to the quantity of heat required during ignition. The results of this computation apply to a highly idealized model of a thermal recovery process. But the results may be used as a guide in engineering consideration of the thermal recovery process. INTRODUCTIO N The thermal recovery of crude oil has received considerable attention since the publication by Kuhn and Kochl of laboratory and field tests of this method of oil recovery. Other publications2,3,4,5,6, since that time have dealt with various features of the thermal recovery of oil and have illustrated the extremely complex nature of this process. Vogel and Krueger7 described an electric analog computer designed to solve a moving heat source problem which was analogous to movement of a combustion front during the thermal recovery of oil. The heat source was maintained at constant temperature and was a cylindrical source of infinite height (no vertical heat loss) moving radially at either constant velocity, or at a velocity inversely proportional to the radial location of the heat source. Jenkins and Ramey2 presented analytical solutions to a similar heat conduction problem and pointed out the possible importance of vertical heat losses. The following presents a general solution to the transient heat conduction problem introduced by Jenkins and Ramey4 as well as numerical solutions for a wide range of conditions possibly similar to those that might exist during field operation of the analogous thermal recovery process. DESCRIPTION OF PROBLEM The problem considered in this paper is determination of transient temperature distribution caused by a cylindrical heat source of infinite or finite vertical height, moving radially through an isotropic medium of infinite extent. It is further assumed that the heat flux generated at the surface of the moving heat source may be a function of time such that the fuel concentration required may be constant, or permitted to vary, and that heat is generated at the surface of the heat source only. In regard to the thermal recovery of oil the assumption that heat is generated at the surface of the front is equivalent to assuming that the thickness of the combustion zone is infinitely small, or that the reaction rate between fuel and oxidant gas is infinite. The last assumption does not appear stringent. See laboratory information published by Martin, et al3 Under these assumptions the temperature distribution throughout an infinite medium caused by a heat source moving radially with an arbitrary velocity may be described by The heat generation function or heat flux at the surface of the source, +(t), is Note that the fuel concentration may be defined as a function of time. Eq. 1 is derived in the Appendix.

By Regis M. N. Pelloux, N. J. Grant

Five or six alloys each in the systems Ni-C.v, Ni-Mo, and NL-W, spaced to cover the single phase areas as well as a part of the adjacent two-phase field, were prepared as uacuum-melted alloys. Tensile tests at room temperature and stress rupture tests at 1200° and 1500°F we.ve run for time periods to give fracture in 0.1 to 500 hr. Observations mere made of solid-solution and second-phase strengthening or uleakening, coupled with studies of ductility and the role of structure on the noted behavior patterns. THE development of stable creep-resistant alloys while broad and systematic is also highly empirical. A number of simple rules have been suggestedL-" but these are based on scant data. Whereas rules for low-temperature alloy strengthening can be applied with some success in more simple systems, the extension to behavior at high temperatures (greater than about 0.4 of the absolute melting temperature) is very poorly understood and has encountered important exceptions and deviations in terms of atom size or valency effects. In particular, the occurrence of both solid-solution weakening4,5 and second-phase weakening2 at high temperatures is of interest. MATERIALS AND PROCEDURE Nickel was chosen as the base material because of its important role in current high-temperature alloy applications, because of its freedom from a phase transformation, and because of wide solubilities for many elements of interest. The selected alloys were single- and two-phase structures in the Ni-Cr,6 Ni-Mo,7 and Ni-w 8 systems. The alloys were vacuum melted and cast, utilizing high-purity raw materials, in the form of 15 lb ingots. They were readily forged into 1/2-in. bar stock (except the two highest chromium alloys). The alloy compositions are shown in Table I. Typical impurity values are: Carbon: Max 0.03 pct (except for 30 and 35 pct Cr alloys which had 0.07) Nitrogen: Max 0.005 pct (except for two of the Cr alloys which had 0.05) Sulfur: Max 0.004 pct Silicon: Max 0.05 pct Each alloy was solution treated (air quenched) to produce comparable grain size. The two-phase alloys were then overaged in an effort to produce a stable structure for testing at 1200° and 1500°F, The results are summarized in Table 11. Following the heat treatments outlined in Table 11, the bars were machined to a gage section of 1.25-in. long by 0.250-in. diam. In addition to room-temperature tensile tests, stress-rupture tests were run at 1200" and 1500°F for time periods from 0.1 to about 500 hr. RESULTS Room-Temperature Mechanical Properties—The ultimate tensile strength, total elongation, and reduction of area values for all the alloys are plotted vs atomic percent of the solute element in Fig. 1. It can be seen that for the same amount of solute element the ultimate tensile strength increases in the order chromium, molybdenum, tungsten. Elongation increases (reduction of area decreases) with increasing amounts of solute for all the solid solution alloys, the values ranging from 50 to 70 pct. The ultimate tensile strength values for the two-

Jan 1, 1961

By E. C. Hopkinson, A. H. Youmans, R. A. Bergan, H. I. Oshry

A new log has been developed for quantitative formation evaluation which is based on a measurement of the length of time slow neutrons survive before they are captured in the rocks and fluids. The logging instrument employs a cyclically pulsed neutron generator and a gated scintillation counter which is synchronized with the source. The source emits short, intense bursts of 14 mev neutrons once every 1,000 microsec and is quiescent between bursts. During the period the source is quiescent, the detector is electronically actuated for two independent preselected intervals. A comparison of the counting rates during these two intervals gives a measure of the rate of decay of the slow neutrons and of the associated gamma radiation. The average neutron lifetime in most earth formations is in the range from 50 to 500 microsec. It can be measured during a continuous logging operation at conventional logging speeds. The design of the logging instrument is described and the results of tests are compared with theoretical predictiom. Formulas are developed which give the relationship between log response and formation properties. It is shown that the method is particularly sensitive to formation fluid salinity, and that salt water saturation can be measured accurately in either cased or open hole. The measurement can be made independent of borehole size, fluid type, casing and tool position in the hole by properly selecting the intervals during which the measurements are made. The results of tests with a prototype logging tool are given. INTRODUCTION A new nuclear logging system has been developed which employs the Accelatron,* an accelerator-type neutron source, and accurately measures formation brine saturation in an entirely new way. It has produced a type of formation log with better sensitivity, greater sampling depth and simpler quantitative interpretation than any other nuclear log thus far suggested. The new Neutron Lifetime Log* employs a pulsed electromechanical neutron source and a synchronously gated radiation detector. A prototype instrument has been field tested during recent months to demonstrate the operability of the apparatus and the feasibility of the method. Tests in wells and simulated boreholes have confirmed theoretical predictions and have shown that formation param ters can be measured independent of casing and other borehole parameters. Preliminary results of field tests have indicated that the log may have important and widespread applications. BASIC PRINCIPLE OF NEUTRON LIFETIME LOG The Neutron Lifetime Log is based on the fact that neutrons emitted by a source in a well are rapidly but not instantly captured by the material around the source. Their capture is a matter of statistical probability; the greater the number of capturing nuclei and the greater the "capture cross section", the greater is the probability that a neutron will be captured quickly. The average life of a thermal neutron in vacuum is about 13 minutes, but in common earth materials, the average neutron life ranges between extremes of about 5 rnicrosec for rock salt and perhaps 900 microsec for quartzite. The Neutron Lifetime Log responds to variations in this average neutron life. The theoretical basis for a log of this general type has been well understood by nuclear logging experts in many laboratories both in America and in Russia, and develop mental work along these lines has been in progress for many years. The Russian literature has reported both theoretical and experimental work1,2 but in this country there have been no published reports of progress toward a practical logging instrument. The logging instrument is designed to measure radiation produced by slow neutrons during selected intervals when no neutrons are being emitted by the source. The source is arranged to emit neutrons in bursts or pulses. During the quiescent interval between the pulses, it is possible to observe the exponential "decay" of the neutrons and the neutron-induced radiation as the individual neutrons progressively disappear due to capture by atoms in the formation or the borehole. When a short pulse of 14 mev neutrons is emitted by a source in a borehole, the individual neutrons are slowed to thermal energy within a few microsec. Thus, a cloud of "slow" neutrons is formed around the source within 10 to 50 microsec after the pulse. This cloud is most dense within a few inches of the source, and is progressively less dense out to a radius of about 3 ft, where radiation from the source is practically undetectable.

Jan 1, 1965