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By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By C. E. Turner, J. R. Elenbaas, R. D. Grimm, J. A. Vary, D. L. Katz

A technique is presented by which well samples and core plugs of dolomite formations are classified by microscopic examination into seven different porosity grades. Quantitative values of porosity and permeability are determined for each grade by a statistical correlation of the core plug test data with the porosity grading system. These quantitative values are applied directly to the grades exhibited in the well samples for the purpose of estimating the reservoir void space for wells that were not cored. The procedure is described for estimating the gas reserves per unit area lor the South Hugoton gas field. but a reserve estimate for the field is not given. INTRODUCTION The miscroscopic examination of well sample; and the graphic recording of their lithologic qualities and other distinguishing characteristics of various geologic formations drilled is both a science and an art of long standing and wide application. Usually the primary objective of a geologist who "sits on the well" and examines the samples are: to identify the formation being drilled, determine the total depth, casing point. and completion interval. In most cases the porosity is described. if done at all, in general terms. such as: trace, scattered, fine, poor, fair, medium. good, excellent, or in some other relative terms. In fields where various geologists have examined samples and recorded observations on many wells considerable variations in lithologic terms and porosity descriptions occur unless there is primary effort to establish uniformity of logging observations and standards of recording observable porosity. When an estimate of the pore volume of a reservoir is made a geologic concept of the processes that control the magnitudes of porosity and permeability is developed by microscopic examination of well samples. The characeristics and appearances are then mentally related to rather general quantitative units of porosity based on physical core data from the same reservoir or on such data or experience in other reservoirs that have similar qualities. The reliability of such estimates depends largely on the variations of the lithology of the formations, the geometric properties of its void system. the extent of comparisons of sample appearances with porosity data, as well as the uniform recording of all relevant characteristics. This statement is particularly significant for dolo-mitized limestone formations of substantial thicknesses and heterogeneity such as the Permian Dolomites of the Hugoton gas field. Jn this field, as well as in most of the Permian Dolomite fields, the producing formations are of relatively great thicknesses in which the porosity and permeability of the reservoir varies substantially in all directions, depending on the crystalline structure. degree and kind of impurities, kind of fossils anti cementation thereof, degree of dissolution. and fracturing. The variations of the lithologic texture of the dolomites and post deposition alterations have resulted in porosities and permeabilities of such magnitudes that only a part of the gross thickness can be counted as "pay." At the time of this study insufficient gas production had been experienced to apply the pressure decline production method in the South Hugoton Field and the electric logs are not definitive enough. The problem of estimating gas reserves in the south part of the Hugoton Field is primarily one of determining the pay thickness and porosity from well samples and core data. The area studied embraced all that part of the field lying south of an east-west line through Guvmon, Okla., anti containing approximately 1.000,000 acres. This paper describes a technique of correlation of physical core data with well samples so that quantitative values of pay thickness, porosity. Permeability, and connate water may be assigned to well samples that are representative of a given interval, and thereby permitting the estimation of gas reserves lor a given unit area. The procedure was developed by a uniform microscopic qualitative porosity grading of the dolo. mite core plugs.. and relating these grades to the respective physical core data on a statistical basis The well sample-were also graded in a Similar manner in order that the quantitative values established lor the core plugs could be applied to the well Sample for wells that were not cored. GRADING OF DOLOMITE A group of experienced geologists was given the assignment of examining the samples on all wells in South Hugoton in order that they could log their observations in a uniform and standardized manner and grade the observed porosity so that it could be related quantitatively to the core data. The group initiated the study 011 chips from cores which bad been tested for porosity and permeability. This study continued until all of the geologists developed a common knowledge of lithologic terms and of the characteristic appearances of the samples and their relations to measured porosity. The characteristic appearances of the dolomite samples under twelve-power magnification as related to their qualitative porosities afforded a classification of the dolomite into :even grades of porosity, ranging from dolomite of no-visible porosity under twelve-power magnification to dolomite of excellent porosity. The assigned grade for a specific 10-ft interval is a weighted average of all visible grades of porosity exhibited by the cuttings representing that interval. The porosity characteristics were recorded by a color graph adjacent to the lithology column in conjunction with a numerical system for further definition of relative porosity as shown in Fig. 1. The three vertical lines to the right of the lithology column each represent 33 1/3 per cent. which lines were used to record the percentage of the samples, for any particular interval. that showed porosity under the microscope. The colors were used to denote actual pore size. i.e., orange. blue and I-ed for pore diameter of one-fourth or less. one-fourth to one-Ilalf. and greater than one-half millimeter, respectively. The area colored 1)). one or more colors represents the percentages of the samples exhibiting pores of the respective size or sizes. The numerals from one to six inclusive shown on the log in

Jan 1, 1952

By D. J. Carney, J. Chipman, N. J. Grant

An absolute calibration has been achieved for sampling and analyzing liquid steel for hydrogen based on Sieverts&apos; values of hydrogen solubility in iron. Further checks were made in nickel, iron-nickel, and 18-8 stainless melts. The sampling method was successfully applied to a large number of commercial steel melts in various types of furnaces. The concurrent problem of sample storage was also solved. THE problem of sampling of liquid steel for hydrogen is more difficult than the problem of analysis. Hydrogen has a greater mobility than any other element; it is the only element that will diffuse out of steel at room temperature. In accordance with the known relation between temperature and diffusivity, the diffusion of hydrogen is extremely rapid at the temperature of liquid steel. Consequently, in the past, attempts to quench molten steel to retain the dissolved hydrogen have not been as successful as similar attempts with nitrogen or oxygen. The retention of hydrogen is especially difficult since it will continue to escape at room temperature even if the molten metal has been rapidly quenched. The hydrogen sampling methods may be classified broadly as (1) the rapid quenching techniques which attempt to preserve super saturation and (2) those methods which attempt to collect the gases evolved as the metal freezes and cools to room temperature. With all methods of sampling but especially with the rapid quenching methods, there is also a concurrent problem of storing the sample until analysis is undertaken. The two problems are interrelated and must be considered together when discussing liquid steel sampling techniques. The major obstacle in liquid steel sampling has been that there was no way of evaluating properly the various sampling and storage techniques which have been developed. It has not been possible to compare the accuracy of the various methods. For evaluation of sampling methods some known standard is required; this may be found in the published work on the equilibrium solubility of hydrogen in liquid iron which has been determined in three separate investigations.1,2,3 The data are shown in table I. Sieverts&apos; original method of obtaining gas solubilities involved measurement of the volume of gas required to saturate the liquid metal contained in an evacuated bulb of known volume. This procedure, improved by introduction of high frequency induction heating, has yielded reproducible results which appear to be entirely dependable. Using Sieverts&apos; method, it has been proved for iron and other metals and alloys that the hydrogen solubility is proportional to the square root of the pressure of the hydrogen gas above the liquid, so that one may work with various partial pressures of hydrogen to put different amounts of hydrogen in solution. From Sieverts&apos; law it is possible to know accurately what amount of hydrogen is dissolved in the liquid metal at the time of sampling. The accuracy of a sampling method may be gauged by reference to this known solubility. It was the purpose of this investigation to develop a method for sampling liquid steel and for storing the sample so that the analytical result would represent the actual hydrogen content of the metal bath. For this purpose an induction furnace was

Jan 1, 1951

By John G. Tate, George W. Nicolson, James L. Bruce

FOR more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.1 From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. DESCRIPTION OF ORE BODIES The shape of the ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions, extending from unknown depths below the bottom level at elevation 250 ft below sea level, to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the ore body extended to surface and was mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upperside of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and clay sedimentaries of Miocene and later age. The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-stained by the descending meteoric waters. It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pct Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pct. On the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. Some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. This probably can

Jan 1, 1947

By P. P. Scott, George C. Howard

A field remedial procedure utilizing a kerosene-cement slurry as a water plug-off agent in fractured formations was evaluated both in the laboratory and in the field. This procedure has proved to be capable of effectively shutting off water without causing permanent impairment of the oil production. Success was attributed to the fact that an immobile cement slurry, when placed in a water-producing strata, will set and form an impermeable barrier; whereas when placed in an oil-producing section the cement will retain a relatively high permeability and may be removed by acidizing. INTRODUCTION One of the most perplexing problems facing the oil industry is the selective exclusion of water production from oil or gas-producing wells. This problem has been studied by many investigators in an attempt to develop a material that is not only capable of reducing water production but is also capable of being selective in that it will not impair oil production in either fractured or intergranular type reservoirs. A study of these two types of formations indicated that two distinct types of materials for controlling water production might be required — a completely liquid plugging agent for intergranular formations and a semi-liquid or slurry type plugging agent for fractured formations. This paper is limited to the control of water production from fractured formations. A common source of water in the vicinity of oil bearing rock reservoirs is water which previously has entered and, because of its higher density, generally lies near the bottom of the formation. When the deepest point of penetration of a well into such an oil and water-bearing formation is above the level of the water, and the dynamical gradients due to the flow of oil overbalance the difference in densities between oil and water, water production becomes a problem. Then the water level rises in the shape of a cone and is produced from the lower depths. Other investigators1,2,3,4 have developed theories which define the pressure gradients and contours of this cone in a homogeneous formation and have shown that the placement of a plug in the bottom of a well is only slightly effective in temporarily reducing the flow of water. Assuming that the manner of flow of bottom water from fractured formations to a well is generally similar to the flow in homogeneous formations, then it would be expected that some form of coning, perhaps of less symmetry, would also occur. Then, because of the similarity of the manner of flow of water, placement of a vertical plug in a fractured formation would also probably be ineffectual for controlling water production. However, as has been shown by electric model flow study,&apos; the placing of a plug in a well and an impermeable horizontal streak in the formation might prove to be a means for materially reducing or even eliminating water production in a fractured formation. An indication of the difference in effectiveness between horizontal and vertical plugs based on theory developed from study of the flow of water and oil in rock reservoirs is depicted in Fig. 1. These curves show the expected

Jan 1, 1955

By C. F. Rust

Experimental evidence is presented showing that reproducible formation resistivity factor measurements and resistivity index determinations on reservoir core samples map be made utilizing either the two- or four-electrode methods. Equipment is described which permits the application of either technique to the core specimen without loss of time and with a minimum amount of effort. Since electrical resistivity measurements on reservoir rocks are important not only in electric log interpretations, but also in the study of fundamental rock parameters, it was considered desirable to compare the applicability of both techniques of resistivity measurement. INTRODUCTION The techniques employed in the measurement of electrical resistivity on reservoir rocks, as practiced in the petroleum industry, may be reduced to two fundamental methods: one utilizing two electrodes only, usually referred to as the two-electrode method; the other using two additional electrodes and commonly known as the four-electrode method. In the former, the core sample whose resistivity is to be measured is mounted between two electrodes, usually metal discs, which serve to pass a current of known magnitude through the saniple. The potential drop across the sample, measured between these same two electrodes, and the core dimensions furnish the necessary data to compute he resistivity of the sample. In the four-electrode technique the end plates, again usually ol metal, still serve as current electrodes. Additional probes or electrodes dispersed along the sample are utilized to measure the potential drop. Both methods are used in practice1,2 and it is the purpose of this paper to compare the two techniques as applied to the determination of formation reiistivity factors and the resistivity index exponent n, in Archie&apos;s empirical equation I = p/po = Sw 11. To evaluate the two techniques it is desirable to point out the experimental precautions which must be taken to insure reliable results. It is evident from the electrode arrangements of the two- and the four-electrode methods that, for a given sample, the volume of sample included by the four-electrode method is less than the volume included by the two-electrode method. One of the prime difficulties associated with the two-electrode method is the possible occurrence of an abnormally high resistance between the electrodes and the brine-saturated sample, which results in erroneous resistivity values for the core sample itself. Attempts to alleviate this difficulty meet varying degrees of success. Methods used in the past employ such absorbent materials as brine-saturated Kleenex: chamois, or felt. A technique described by Morgan, Wyllie, and Fulton,1 appears to be more satisfactory. Their method consists of spraying or painting the end areas of a core sample with conductive silver paint. This technique reduces contact resistances between the porous medium and the electrodes to a value which is generally negligible as compared to the resistance of the sample itself. In the four-electrode method these requirements are not as stringent since separate probes are used to measure the potential difference acrozs a portion of the sample. In this case, contact resistance occurring at the current electrode; are of no consequence. and those appearing at the potential

Jan 1, 1952

By E. E. Donath

THE coal hydrogenation process is well known as a means for the production of liquid fuels -from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aromatics and of tar acids and tar bases. The relative amounts of heavy and middle oil-boiling above and below, e.g., 325°C-can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.1 Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydro¬gen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catch-pot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1952

By D. Turnbull, R. E. Cech

EXPERIMENTAL studies of precipitation of iron from solid solution in copper by Gordon and Cohen 1, Bitter and Kaufmann 2 and Smith 3 revealed that the precipitate particles were initially paramagnetic but could be changed to a ferromagnetic

Jan 1, 1955

[PRESIDENT AND DIRECTOR H. G. MOULTON3 NEW YORK, N. Y. PAST PRESIDENTS AND DIRECTORS - D. C. JACKLING1 SAN FRANCISCO, CALIF. DONALD B. GILLIES2 CLEVELAND, OHIO TREASURER AND DIRECTOR KARL EILERS3 SEA. CLIFF, N. Y.]

Jan 1, 1940

By D. D. Todd, W. A. Oates

THERMODYNAMIC data for solutions are best derived from a combination of equilibrium and calorimetric studies. However, the accurate measurement of heats of mixing of metallic solutions at high temperatures presents considerable experimental difficulties, simple calorimeters1-3 giving

Jan 1, 1964

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10&apos; cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;&apos; the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson&apos;s equation is

Jan 1, 1965

By Philip R. Strand

Vermiculite is the name used for those micaceous minerals with a ferromagnesian aluminum silicate composition and the unique property of exfoliating to a low density material when heated. Commercially, the exfoliated products are also called vermiculite, or more exactly, expanded vermiculite. In its exfoliated state, vermiculite serves many markets, chief among them construction, agriculture, horticulture, and general industry. Composition and Properties Vermiculite, in a natural state, has the characteristic mica habit, splits readily into thin laminae, flexible but inelastic. In a mineralogical sense, vermiculite is a hydrated silicate with no exact chemical composition. The structural formula for a macroscopic, trioctahedral vermiculite may be written: [ ] The structure of vermiculite is basically that of a talc, and it could be regarded as a trioctahedral member of the smectite group. Macroscopically, vermiculite displays the prominent monoclinic crystal faces that are commonly marked by lines at 60° and 120°. Hardness varies from 1.5 to 2.8 or more; specific gravities are between 2.1 and 2.8; color is amber, bronze, brown, dark green, or black. When heated quickly to an elevated tempera¬ture, vermiculite expands by exfoliating at right angles to the cleavage, into wormlike pieces (the name vermiculite is derived from the Latin `vermiculare,&apos; to breed worms). This characteristic of expansion, the basis for commercial use of the mineral, is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The increase in bulk volume of commercial grades is 8 to 12 times, but individual flakes may expand as much as 30 times. All expansion occurs at right angles to the basal cleavage. Vermiculite may also be expanded by a number of chemical processes such as soaking in hydrogen peroxide, weak acids, and other electrolytes. There is a color change during expansion that is dependent upon the composition of the vermiculite and furnace atmospheres. Heating in an oxidizing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. The exfoliation of the vermiculite crystal results in large pores being formed between groups of platelets. Thus exfoliation can make available a large increase in void volume without significantly changing the surface area of the platelets. This characteristic is important in the chemical carrier applications of vermiculite. Although there has been much research on the chemical and structural composition of vermiculite, an exact formula and composition cannot be described. This is to be expected since vermiculite derives from a number of different mineral sources. As has been proposed, vermiculite is not a single mineral species, but families of related minerals. Additionally, commercial interest in the end product has resulted in the name vermiculite being applied to the very voluminous, bloated products from calcination of baueritized (bleached) phlogopite. This has also resulted in many names for the specific vermiculite found in a particular deposit. All of this difficulty arises from the nature of its crystal chemistry. Consequently, vermiculite is now thought of as several related variable mineral series rather than a group of related species. The vermiculites have a common silica tetrahedral sheet structure with separating ions. It is now generally agreed that vermiculites must also be regarded as true clay minerals. The properties of the mineral, such as cation exchange capacity, organic complexing ability, and vari-

Jan 1, 1975

By John F. Lundeberg

CLAUSS1 observed that if isothermal creep data could be approximated as straight lines on a log stress-log time plot, a relationship existed that could be expressed as log t = m log s + b [ l] where t = time,

Jan 1, 1965

[Officers and Committees of the Society of Petroleum Engineers 1 Officers and Staff of the AIME 2 Officers of AIME Sections Predominantly Petroleum in Membership 3 Alphabetical List of Members 5 Geographical List of Members 106 Advertisers&apos; Index 128]

Jan 1, 1961

[Officers and Committees of the Society of Petroleum Engineers 1 Officers and Staff of the AIME 2 Officers of AIME Sections. Predominantly Petroleum in Membership 3 Alphabetical List of Members 5 Geographical List of Members 95 Advertisers&apos; Index 122]

Jan 1, 1961

By H. E. Stauss, G. Sandoz

AN increase in the value of magnetostriction1 * is known to result from the annealing of some ferromagnetic alloys in a magnetic field. Similar increases may be anticipated in the value of the magnetostriction of alloys that are of interest because of their normal high values. Two were selected for trial, 87 pct Fe-13 pct Al(Fe,Al) and 69 pct Co-31 pct Fe, the latter being used as a representative of the Co-Fe alloy series. The influence of a magnetic field present during annealing is explained by the domain theory of magnetism." The field orients the domain vectors in its own direction when the alloy is at or below the Curie temperature, and holds them there until the metal is cold. During cooling the interaction stresses between neighboring grains are largely relaxed. Interaction stresses will reappear, however, if the state of magnetization of the specimen is changed in any way, and will be larger the more the new state of magnetization differs from the one existing during the magnetic anneal. In this connection the 180" reversal of a magnetization vector is not considered a change because a simple reversal does not tend to produce a change in shape of a magnetized region. When the field existing during the anneal is removed after the metal is cold, the domain vectors can turn back only to the nearest crystallographic directions of easy magnetization because return to random

Jan 1, 1953

By Frank D. Hoyt

BY far the most conspicuous of the Pennsylvania slate districts is that extending from the New Jersey line at the Delaware Water Gap westward almost to the Schuylkill River. This covers parts of three counties in east-central Pennsylvania: Northampton, Lehigh, and Berks. The most important development, both in geographic size and product importance, is in Lehigh and Northampton counties. The greater part of the region is underlain by only one formation-the Martinsburg, consisting of slates, clay slates, and sandy shales, all of the Ordovician period. The slate-bearing Martinsburg formation is underlain by Cambro-Ordovician limestones. Immediately overlying the Martinsburg formation is the Tuscarora quartzite of the Silurian period. The Martinsburg formation itself is divided into three distinct divisions, termed simply: the upper, the middle, and the lower members. Commercial slate has been extracted from all of these members, but the formation of greatest importance is the upper member, representing 2600 ft of the total formation thickness of nearly 11,000 ft. The upper member is commonly referred to as the "soft slate" and consists of three facies: 1) beds of blue-gray, very sandy, almost quartzitic slate, in many places, approximately a medium-coarse sand- stone with calcareous cement; 2) blue-gray sericitic slat-the dominant rock type of this member-with occasional chloritic beds; and 3) dark gray or virtually black, highly carbonaceous beds, referred to locally as "ribbons."

Jan 8, 1958

By Alan D. Randolph

INTRODUCTION The production of fines is an unwanted side-effect in most crystallization processes. The definition of “fines" is relative to the size of the desired product and varies from <30 mesh for coarse KC1 fertilizers to subsieve organic material produced by salting-out pro- cesses. Sometimes a well-developed fines distribution is necessary in the production of large crystals, e.g. the fines removal stream from a potash crystallizer. The production of fines is usually not desired in a crystallization separation step. However, product purity can either improve or degenerate with a decrease in crystal size depending on the relative importance of product washing vs mother liquor occlusions in determining over-all purity. Typically, both washing efficiency and mother liquor occlusions decrease with decreasing particle size. Fine crystal distributions have historically been difficult to measure and categorize; however this situation is changing rapidly with the use of electronic particle counters of the electrical zone- sensing or light scattering type. In fact, fine-crystal measurement is perhaps the key to better understanding and control of coarse- crystal crystallization processes. The fine-crystal distribution carries much useful information from which nucleation and growth rates can be inferred. The purpose of this paper is to briefly discuss a few crystallization processes in which production and/or measurement of fines is important and to categorize the process conditions which yield a fine- crystal product.

Jan 1, 1980