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By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By J. E. Lawrence

Copper-decorated lattice disorders in silicon have been analyzed by electron transmission microscopy, chemical etching, and P-N junction reverse current measurements before and following different gettering treatments. Lattice disorders acted as the nucleating sites for copper precipitation. Copper precipitates in silicon resist chemical etching, absorb electron beams more than silicon, and cause excess reverse currents. Totally gettered disorders will chemically etch rapidly, be transparent to electron beams at extinction contrast, and not contribute to excess reverse currents. Three different gettering procedures were performed to determine the effectiveness of different EXTRANEOUS metal contamination can alter the minority carrier lifetime and resistivity of bulk silicon as well as cause excessive reverse currents in semiconductor devices. Previous workers have reported such activity for gold,1,2 copper,'-* iron,' and rnanganese.2,5 Gettering is a method employed to render these impurities electrically inactive. However, some property of the junction-degrading metals prevents gettering procedures from being wholly reliable. The comparative effectiveness of gettering with different agents has been the topic of earlier publications.2,3,6-11 Two mechanisms for gettering metallic impurities have been proposed: the distribution coefficient mechanism by Thurmond and Logan7 and the compound formation mechanism by Goetzberger and Shockley.2 Both of these models evolved from data gettering mechanisms. First, phosphorus was allowed to enter a protective SiO2 film but remain away from the Si-SiO2 interface to test the effectiveness of the compound formation gettering mechanism. Second, phosphorus was allowed to enter the backside of silicon wafers to test the effectiveness of the lattice strain gettering mechanism. Finally, nickel was diffused into the backside of silicon wafers to test the effectiveness of the distribution coefficient gettering mechanism. In each case, copper precipitates dissolved as a result of the gettering treatment. Tightly packed precipitates will resist gettering more than loosely packed copper precipitates. acquired by the electrical analyses of gettered semiconductor materials. An electrical analysis, however, cannot identify the fate of the gettered metals. The radiotracer technique has recently been applied to determine the redistribution of metals following different gettering treatments.3,9,10 The spatial resolu tion of the radiotracer technique prevented the analysis of metal precipitates which contribute to the excessive reverse currents of P-N junctions. The gettering processes employed by the earlier workers, almost without exception, allowed the gettering agent to enter the silicon lattice. This procedure makes it quite difficult to differentiate between the distribution coefficient and the compound formation mechanisms. The metallographic analysis of gettered copper precipitates discussed in this work supplements the earlier work by obtaining direct evidence of silicon lattice defects decorated with copper before and following different gettering treatments. The effectiveness of a process which restricts the gettering agent, phosphorus, to a dielectric film and thus away from the silicon lattice is discussed in addition to the ef-

Jan 1, 1969

By Ronald E. Feltman

Most engineering firms engaged in the design and manufacture of milling components and systems have established, through the years, a relatively well defined system design procedure. The process design engineer has at his disposal several alternative approaches to the successful completion of this task. Unfortunately, while these alternatives, at first glance, appear to be rather straight Forward, any attempt to implement them into a fully integrated commuter design program becomes increasingly more complex when one addresses himself to the problem in total. This paper summarizes Kennedy Van Saun's approach to the solution of this problem through a planned system design. Following the problem definition and discussion, a detailed analysis and system design synthesis is presented; the major aim here being to provide a system design which may be programmed and run on a relatively inexpensive computer installation such as the IBM 1130 system currently in use at Kennedy Van Saun. A summary section is also included, which Provides a general outline guide to the program systems design of equipment which, while quite different from milling system functionally, nevertheless lends itself to the approach used in this paper.

Jan 1, 1969

By P. M. Kelly, E. P. Butler

Four Mn-CLL alloys, containing 60, 70, 80, and 90 pct Mn, respectively, have been examined in the quenched and the quenched and aged conditions using electron microscopy and electron, neutron, and X-ray diffraction. After certain heat treatments the alloys transform from fee to fct and in the tetraom1 condition show a domain structure parallel to {101} planes. Neutron diffraction indicates that the domains are antiferrornagnetically ordered. The domain boundary contrast has been examined using bright- and dark-field microscopy, and the contrast effects observed under favorable conditions have been used to deduce the c axis orientation in each domain. The domains are extremely mobile and can be nucleated at precipitate particles and screw dislocations. The domain mobility is responsible for the high damping capacity. In the aged material a Mn precipitates in the Kurdjumov-Sachs orientation and results of both electron microscopy and neutron diffraction indicate that the matrix separates into two components—one rich in manganese and the other rich in copper. ALLOYS of manganese and copper have the unusual combination of a high damping capacity and good mechanical properties and have been the subject of a number of investigations as part of a general interest in high damping capacity alloys for engineering purposes.&apos;,&apos; SO far, however, there has been no reported electron metallographic study of these alloys. The Mn-Cu system has an extensive range of solid solubility at high temperatures, and the equilibrium phases are expected to be y (fee) and a Mn. The high damping capacity is associated with a metastable tetragonal structure of variable c/a ratio, which forms from the high-temperature y phase. This latter phase becomes more difficult to retain as the manganese content increases, and alloys containing more than 82 wt pct Mn undergo a reversible martensitic fcc — fct transformation on quenching. The X-ray work of Basinski and christian3 showed that the Ms temperature for the transformation was below room temperature for alloys in the range 70 to 82 pct Mn and increased linearly with manganese content. When quenched from the y region, alloys in the range 50 to 82 pct Mn are cubic at room temperature, but become tetragonal if aged at temperatures between 400" and 600°C. The martensite transformation occurs on cooling from the aging temperature. Tetragonal alloys have a banded microstructure and the bands analyze to be traces of (110) planes. Similar microstructures have been observed in In-Tl4 and in other manganese-base systems, such as Mn-Au5 and Mn-Ni.6 The mobility of the bands in Mn-Cu alloys can be demonstrated by optical examination of a polished specimen surface subjected to a cyclic stress.7 The bands appear and disappear as the stress is varied, and X-ray measurements of the (200,020) and (002) peak intensities confirm that a reversible reorientation of the tetragonal structure occurs. Meneghetti and sidhu8 investigated the magnetic structure of Mn-Cu alloys and found antiferromagnetic ordering in furnace-cooled alloys of composition >69 at. pct Mn. Magnetic super lattice reflections occurred at the (110) and (201) positions and the proposed structure was fct with the spins along the c axis. A more complete investigation by Bacon et al.9 confirmed this structure. The magnetic ordering temperature Tn was found to increase linearly with manganese content in the same way as the Ms temperature, and at any composition, Tn > Ms. This relationship suggested that the magnetic ordering was responsible for the cubic — tetragonal transformation in the manganese-rich alloys. The purpose of this investigation was to study the mechanism of high damping and the structural changes that occur on aging. The main technique used was transmission electron microscopy, but X-ray and neutron diffraction experiments were also carried out. EXPERIMENTAL Materials and Heat Treatment. The four alloys, provided by the Admiralty Materials Laboratory. were of nominai composition 60, 70, 80, and 90 Mn and all had low impurity levels, <0.05 pct C, <0.2 pct Fe. This material was cold-rolled to 200-µ strip with intermediate annealing and then given a final heat treatment of 24 hr in the range 800° to 900°C followed by water quenching. An identical heat treatment was given a length of 3/4-in.-diam bar of the 70/30 alloy from which the neutron diffraction specimens were machined. It was suspected that the tetragonal structures would be metastable at room temperature, and so the alloys were not aged until required for experiments. After aging in a salt bath the alloys were water-quenched. Thin Foil Preparation. Initial thinning to 50 to 75 µ was possible in a solution consisting of: 50 ml nitric acid 25 ml acetic acid 25 ml water The surface deposit and grain boundary etching was removed by a final electropolish at around 20 V in an electrolyte consisting of:

Jan 1, 1969

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.&apos; : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*&apos;" Exotic recovery processes have been considered primarily for &apos; perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969

When a thin film of volatile matter is deposited under vacuum on a polished coal surface, and the coated surface is examined microscopically in piano--polarized reflected light, colour changes are observed characteristic of the various macerals present. The colour changes appear to be mainly due to interference between light reflected at the upper surface of the film and at the film/coal interface. A variety of source materials for the volatile matter required have been tested, including powdered bituminous coal, coal tars, boron oxide, and certain resins.

Jan 1, 1969

By R. A. Wattenbarger, H. J. Ramey

A systematic study has been made of the application of the real gas pseudo-pressure m(p) to short-time gas well testing. The m(p) function can be used in real gas flow problems to account for the variation of viscosity and z-factor with pressure. A mathematical model was solved numerically to generate solutions of various real gas flow problems. The effects of turbulence, formation damage and wellbore storage were included in the model. The analysis of simulated well tests showed that the interpretation methods normally used for liquid flow are generally accurate when the m(p) is used. For practical rates without turbulence, the solutions are not rate-sensifive, and the flow capacity.. kh and skin effect can be determined accurately from either a buildup or a drawdown test. However, the kh calculated from a drawdown test can be significantly low when turbulence is present. A case was simulated in which this error wa.s 36 percent. Turbulence does not affect the determination of kh from buildup tests. The proper determination of kh from p and pa buildup and drawdown plots is developed by analyzing their relationship to the m(p) method. A simple equation is given that can be used for long-range gas well performance forecasting. This expression is compared with a method pre-sended by Russell et al." Introduction The formation flow capacity and wellbore damage condition can be determined for liquid-producing tests by means of buildup and drawdown tests. These tests make use of short-time pressure transient data rather than stabilized flow tests that are often used for gas well testing. Tracy&apos; presented a method of gas well testing that was based on ideal gas equations and utilized p2 buildup plots. This method was shown to be good for low pressure wells. MatthewsZ suggested plotting p and using an average slope and average gas properties. This method was more successful on high pressure wells. Al-Hussainy, Ramey and Crawfordh howed that variation in gas properties could be simplified by using the real gas pseu do-pressure m(p). Some cases showed that the use of the m(p) function Original manuscript received in Society of Petroleum Engineers office Aug. 8. 1967. Revised manuscript received June 11, 1968. Paper (SPE 1835) was presented at SPE 42nd Annual Fall Meeting held in Houston Tex., Oct. 1-4. 1967, and at SPE 4th Annual Eastern Regional ~eetin$ held in Pittsburgh. Pa., Nov. 2-3. 1967. 0 Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. &apos;References given at end of paper. provided an accurate method of interpreting buildup and drawdown tests. Because the work of Al-Hussainy et al. included only a few actual cases, there was a need to explore the use of the m(p) method for a greater variety of flow conditions. The occurrence of turbulent flow around the wellbore often is an important factor in gas well testing. Swift and Kiel,&apos; and Carter et a1.&apos; treated turbulence in gas well testing, but did not consider the variation of viscosity and z-factor with pressure. This paper presents the results of an investigation of the application of the m(p) method to buildup and drawdown testing. Vhe investigation included the effects of turbulence, formation damage and wellbore storage. Gas Flow Equations To formulate the mathematical model, many of the assumptions usually used in well testing theory are applied. The system has radial geometry with a closed outer boundary and is composed of a horizontal porous formation that has uniform and isotropic rock properties and uniform thickness. Allowance is made, however, for a radial region of reduced permeability near the wellbore. This region represents formation damage. The geometry of the system is shown in Fig. 1. Darcy&apos;s law does not always apply to gas flow. A more general expression is needed for non-Darcy, or "turbulent" REGION OF DAMAGED PERMEABILITY SEALED BOUNDARIES ClRCULAR WELL BORE Fig. 1—Radial flow model. AUGUST, BT7

Jan 1, 1969

By William J. Bronkala

One of the oldest tools used in mineral concentrating is the magnetic separator. Virtually every mineral handling system has need for some type of magnetic equipment in two types of basic usage. 1. Equipment protection through tramp iron removal. 2. Mineral concentration based on magnetic properties of the minerals contained in the ore.

Jan 1, 1969

By d&apos, C. Antonio, S. H. Reichman

In the course of our studies of the annealing behavior of vapor-deposited silver films we have determined the electrical resistivity as a function of annealing temperature for films in the thickness range of 630 to 3240A. Fig. 1 shows the resistivity of the silver films vs film thickness in as-deposited and annealed conditions. The films were prepared by depositing 99.999 pct pure silver from molybdenum boats onto Vycor substrates. Deposition was conducted at a residual pressure of 5 x 10"6 Torr at rates of 20 to 408, sec-&apos;. Thicknesses were determined using a multiple-beam interferometer. During annealing, resistance was measured using the four-probe method. Measurements were made every 5°C during two consecutive anneals to 300°C under a continuous vacuum of 2 x X6 Torr. The heating and cooling rates during annealing were approximately l° and 2°C min-&apos;, respectively. Typical resistivity vs temperature curves are shown in Figs. 2 through 4. There is an inflection point evident at 120°C on Fig. 2, the first anneal of a 3240A film. This inflection point was found on all films above approximately 1!00A on both first and second anneals. Below 1400A the inflection occurred at approximately 180°C. Figs; 3 and 4 show the first and second anneals of a 1370A film. The inflection point occurs at 180°C on the first anneal and approximately 120°C on the second. Our interpretation of this phenomenon is based on oxygen liberation from the film surface. It is well-documented that the presence of oxygen on silver surfaces causes a reversible increase in resistivity.1"3 The liberation of this oxygen, for example during vacuum annealing, would therefore cause a decrease in resistivity as observed on Figs. 2, 3, and 4 as a change in slope. This is accounted for by the decomposition of Ag20 on the film surface. The free energy of AgzO becomes positive between 125" and 225°C.4 The thickness dependence of the inflection points can be explained as an orientation effect. The films used in this study were preferentially oriented with their (111) planes parallel to the Substrate.&apos;&apos;~ In addition it has been sten that the thinner films, below approximately 1500A, possess a decided "hill and valley"

Jan 1, 1969

This method determines tellurium at concentrations down to 0&#183;01 p.p.m., with geochemical accuracy. Tellurium is volatilized from the rock at 800&#176;C in the presence of sulphur from decomposing pyrite, condensed, dissolved, and finally determined by atomic absorption in a long tube burner. The distribution of Te is shown near some gold lodes at Kalgoorlie. Lastly, a method of synthesizing Te-free pyrite from sulphur and ferrous sulphate is described.

Jan 1, 1969

By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins&apos; calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann&apos;s constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,&apos; the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously&apos; and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By H. T. Kennedy, S. M. Avasthi

An equation developed for gaseous hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 0.73 percent when applied to 264 natural gas and condensate systems including 2,043 PVT points. Another equation developed for liquid hydrocarbon mixtures predicts molal volumes with an average absolute deviation of 1.12 percent when applied to 346 crude oil systems including 1,759 PVT points. Both equations require composition of the mixture to be expressed as mole fraction of methane through heptanes-plus, hydrogen sulfide, nitrogen and carbon dioxide, together with the characteristics of the heptanes-plus fraction in addition to the temperature and pressure. The equations cover wide ranges of the variables involved, and their accuracy is considerably better than that of other available methods. The equations were differentiated to allow calculation of the coefficients of isothermal compressibility and isobaric thermal expansion. (In this paper the coefficient of isothermal com-pressibility and the coefficient of isobaric thermal expansion will be expressed as compressibility and thermal expansion coefficient, respectively.) Equations to calculate these quantities are presented. INTRODUCTION Calculations of reservoir performance for petroleum reservoirs require accurate knowledge of the volumetric behavior of hydrocarbon mixtures, both liquid and gaseous. Compressibilities are required in transient fluid flow problems, and thermal expansion coefficients are important in thermal methods of production. An accurate laboratory investigation of the PVT behavior of each reservoir fluid encountered would be costly and time consuming. For this reason various correlations for predicting fluid properties have been developed and recorded in recent literature. Correlations have been presented in the form of graphs, tables and equations. Since an increasing number of studies are being conducted with the aid of electronic computers, recent efforts have been directed toward development of correla-tions suitable for computer programming. Application of computers permits the use of more complex correlations which otherwise are not feasible. Moreover, methods for predicting reservoir performance, particularly those based on the compositional material balance, depend upon the capability of accurately expressing the molal volumes and other fluid properties as functions of pressure, temperature and composition. The coefficient of isothermal compressibility c is defined by

Jan 1, 1969

By L. G. Austin, R. R. Klimpel

This article demonstrates that the Gilvarry and Klimpel-Austin equations for the random fracture of solids are incorrect by deriving intuitively correct expressions for simple cases and showing that the foregoing equations do not reduce to right answers. It is the purpose of this article to point out serious errors in some existing treatments of the random fracture of solids. Gilvarry &apos; gives the equation where B(y,x) is the cumulative fraction by weight of particles which fall below size y when particles of size x are broken. The constants i, j, k contain shape factors and densities of flaws leading to propagating fracture surfaces. The authors believe this equation to be incorrect. Klimpel and usttin&apos; give where r~ is the number of fracture planes originating from edge flaws (per L where L is the edge length of the original particle), rs is the number of fracture planes originating from flaws on the particle surface (per S where S is the surface of the original particle) and rv is the number of fracture planes originating from flaws within the particle volume. This equation is also incorrect. The failures of these equations will be demonstrated by deriving intuitively correct expressions for simple cases and showing that the Eqs. 1 and 2 do not reduce to the correct answer. In this process, the flaws in statistical reasoning inherent in the derivations of Eqs. 1 and 2 become apparent. THE KLIMPEL-AUSTIN EQUATION Eq. 2 was derived by considering a set number of fracture planes occurring spatially at random within a given particle. This case will be treated here in its simplest form: a line with 1, 2, 3, etc., fractures occurring at random. This is illustrated in Fig. 1, with the original length of the line as Vo. The breakage of a long, thin, brittle fiber is a corresponding physical case, with the volume of a fragment proportional to its length. Assuming independence of the occurrence of the fractures, the probability of any one fracture occurring in length dV is dV/V0. The probability of the first fracture occurring at a length V to V + dV is dV/Vo. For the case of only one fracture per particle, formation of a number-size distribution of the left-

Jan 1, 1969

By G. R. St. Pierre, R. D. Blackburn

Oxygen contents of&apos; liquid-iron alloys saturated with oxides are analyzed. Minimum points observed in particular Fe-X-O systems can be predicled by a simple extension of first-order interaction methods. If minimum oxygen content occurs at N; where r is the ratio of metal to oxygen in the oxide phase. RECENTLY, wisher&apos; reported on solubility measurements of A1203 in liquid iron at 1580°C which support the earlier work of d&apos;Entremont, Guernsey, and chipman2 and Gokcen and Chipman. Swisher&apos;s diagram is reproduced in Fig. l. Minimum points in oxide solubilities have also been found in the Fe-Cr-0 system,4 Fig. 2, and the Fe-Ti-0 system,&apos; Fig. 3. Minima positions can be used to confirm approximately the measured first-order interactions, &, cgr, and E&~, in liquid iron and to deduce compositions of components of constant activity in the oxide phases. Consider the solution of Alz03 in liquid iron: for which an equilibrium constant can be written as: differentiating Eq. [2] with respect to Na~, the atom fraction of &l in the metallic solution, and noting that If the activities of Al and 9 are expanded by a first-order interaction model, then:

Jan 1, 1969

By A. Totani, S. Nakajima, H. Okazaki

The phase diagram for the SnTe-SnSe system has been studied in the temperature range from 300° to 900°C by differential thermal and quenching techniques. The X-ray measurements were made on quenched specimens. High-temperature diffraction was also made to study the phase transition in SnSe. The system is proved to be of a eutectic type in which no intermetallic compound exists. The eutectic point is at the composition SnTeo.55 Seo.45. the eutectic temperature being 755°C. Solid solubility limits are SnTeo.6Seo.r and SnT eo. 3s Seo.6s at the eutectic temperature, and change almost linearly to SnTeo.aaSeo.lz and SnTeo.18 Seo.az as temperature decreases to 300°C. It was shown that the SnSe phase has a phase transition of the second order at about 540°C and that the transition temperature decreases with increase of the SnTe content. THERMOELECTRIC properties of tin telluride (SnTe) and tin selenide (SnSe) have been studied extensively in recent years. The variation of physical properties with composition could be of interest if these compounds form an appreciable crystalline solution. The purpose of present investigation is to confirm the formation of crystalline solution or intermetallic compound, if any, and to establish the phase diagram for this system. The crystal structure of SnTe is NaCl type with a cubic unit cell1 (a = 6.313A). The crystal of SnSe having an orthorh2mbic unit cellz (a = 11.496, b = 4.1510, and c = 4.4437A) is isomorphous with tin sulfide (SnS) which has a distorted sodium chloride structure. It has been known that SnSe has a phase at at 540°C; the transition has been assumed to be of the second order. As far as we know, only two studies on the SnTe-SnSe pseudobinary system have been reported. The conclusion obtained in these papers is that, in the composition regions near SnTe and SnSe, the system forms a crystalline solution of the SnTe structure and the SnSe structure, respectively, and that, in the intermediate region, both phases coexist. However, neither the variation of the solid solubility vs the temperature nor the liquidus and solidus were investigated. Hence present writers have attempted to determine the phase diagram of the system by differential thermal analysis (D.T.A.) and X-ray diffraction. EXPERIMENTAL Sample Preparation. Starting materials, SnTe and SnSe, were prepared by the direct fusion of commercially available high-purity (99.999 pct) elements. Stoichiometric amounts of each couple Sn-Te or Sn-Se were weighed into a clear fused silica ampule. After evacuation to a pressure below 10-3 mm Hg, the am- pule was sealed, and annealed at 900°C for 5 hr. The melt was quenched in water. X-ray analysis confirmed the formation of a single phase of SnTe or SnSe. The other samples, SnTel-,Sex were synthesized from these SnTe and SnSe by mixing them in the required ratio, followed by annealing at 900°C and quenching. These samples were used directly for D.T.A. For X-ray measurements, samples were annealed at 700°, 600°, or 500°C for 100 hr or at 300°C for 150 hr, and then quenched in water. It was found that the lattice constants of the SnTe phase annealed for 150 hr at temperatures above 500°C did not differ from those annealed for 100 hr at the same temperatures. However the X-ray phase analysis showed that at 300°C the annealing for 150 hr was necessary to attain a true equilibrium state. D.T.A. The solid-liquid equilibrium temperature was determined from D.T.A. measurements. The sample was sealed in an evacuated silica tube and molybdenum powders sealed in an another tube were used as a reference material. The sample and the reference tube were placed in a nickel block and were heated from room temperature to 900°C at a rate of 3°C per min and then cooled down at the same rate to 600°C. Thermocouples for these measurements were Pt-Pt. Rh (10 pct) and the error of temperature measurements was within + l0C. D.T.A. curves were obtained on a two-pen recorder and an automatic controller (PID type) was used for the program of heating and cooling. When temperature reaches the solidus from the low-temperature side, there appears an endothermic peak. The solidus temperature was determined by extrapolation of the straight portion of the starting flank of this peak to the base line. In a similar way, the liquidus temperature was determined from an exothermic peak on D.T.A. cooling curve. In the case of supercooling, if any, its degree can be estimated from the magnitude of the abrupt temperature rise. X-Ray . X-ray powder patterns were taken by a diffractometer using CuK, radiation. Since the SnSe crystal is cleaved easily, the powders become flaky when SnSe-rich samples are ground in an agate

Jan 1, 1969

By M. T. Hepworth, A. K. Stewart

Iron containing 0.1 pct A1 and -0.9 pct P by weight was internally oxidized in the temperature range 900° to 1300° C, where the bcc structure is stabilized by phosphorous. By measuring the depth of penetration of oxygen with time in an internally oxidized zone for an imposed surface oxygen potential, oxygen permeability was determined. The dgfusion coefficient of oxygen in iron was then calculated using known solubility data, yielding the expression: where Do is the diffusion coefficient of oxygen in bcc iron in sq cm per sec and T is temperature in OK. RECENTLY Hepworth, Smith, and Turkdoganl measured the diffusivity of oxygen in bcc iron and reported the temperature dependence of diffusivity from data determined in the a, and 6 temperature ranges. Subsequently Swisher and Turkdogan&apos; have measured the diffusivity of oxygen in fcc iron. Internal oxidation techniques were employed by these investigators and in this current study. The analysis of this technique is developed by wagner3 (presented in English by Hauffe4 and Rapp 5). In this present study bcc iron stabilized by phosphorous was used to determine oxygen diffusivity in the temperature range 900° to 1300°C. Meijerin 6 has studied oxygen permeability in this temperature range using bcc iron stabilized with 5 pct Sn. Other inves- tigators who have studied oxygen permeability in bcc iron at other temperatures are Schenck et al., 7 Bohen-kamp and Engell, 8 and Bradford. EXPERIMENTAL Electrolytic iron of 99.99 pct purity was alloyed to contain 0.897 pct P and 0.093 pct Al. The maximum weight percent phosphorous required to stabilize bcc iron between 910" and 1392°C is 0.51 pct as determined by Haughton,10 0.42 pct by Roquet and jegaden," and 0.58 pct by vogel,12 with the latter value preferred by Hansen.13 Microprobe analysis indicated that there was no segregation of the phosphorous either before or after permeability studies; therefore, the quantity of phosphorous added was assumed to be sufficient to stabilize the bcc structure. Furthermore, the permeability results of studies on this alloy agreed substantially with interpolated values from previous data on bcc iron.&apos; An ingot of the Fe-P-A1 alloy was hot-rolled to a l-in.-thick slab. Specimens were machined to dimensions: 13/8 by $ by 1/4 in. The experimental apparatus and procedure used have been described before.&apos; A constant oxygen potential was established by passing argon and hydrogen through a column of oxalic acid dihydrate, which has a water vapor pressure which is well-known as a function of temperature. Slab specimens were exposed to a gas mixture sufficiently lean in oxygen to prevent the formation of a surface oxide for predetermined temperature for selected times. The specimens were then quenched, sectioned, and examined metallo-graphically. All quenched specimens were iron-plated to provide protection from the outside sample edge during polishing. Fig. 1 shows a typical microstruc-ture for a specimen oxidized at 953°C for 48.00 hr at a water vapor-to-hydrogen pressure ratio of 0.20. DISCUSSION AND RESULTS The following equation was derived by Hepworth et al.&apos; from Wagner&apos;s kinetic expressions for internal oxidation:

Jan 1, 1969

By K. E. Manchester, A. H. Clark

Hall measurements have been made on three groups of silicon samples, which were implanted with boron, aluininunz, and phosphorus ions. Boron and phosphorus implants show essentially bulk properties when annealed under previously determined conditions, i.e., 15 min at 80O°C for boron and 10 mirz at 600°C for phosphorus. Bulk properties were also observed in alu?rrilzum-implanted samples when ion concentrations were below 1015 cm-&apos;; however, strange low- terrzperalure behavior and a falloff in cavrier concenlralion was observed for sarnples with ion concenlration abozle loL5 ern-&apos;. This can be attributed to solid-solubility effects since the average bulk concentration f0.r the sample exhibiting bulk properties was below the reported solubility limit for aluminum, while the other samples were above the limit. A detailed study of the annealirzg process indicates that mobilities reach bulk c~alues in phosphorus implants at 250DC, in alutninurn ivnplanls a1 500°C, and in boron implants at 700°C. A simple rnodel has been proposed to fit the annealing data. THE technique of semiconductor doping by direct injection of energetic ions is being actively investigated at this Center. Previously published results from this laboratory have been concerned with the investigation of implanted profiles in silicon and the electrical properties of the resultant p-n structures.1&apos;2 Diode properties have been reported for junctions produced by implantation of boron ions and aluminum ions in n-type silicon and phosphorus ions in p-type silicon. Reverse current characteristics, as well as electron diffraction data, have indicated that the damage to the structure produced by the energetic ions during the stopping process can be minimized by a gentle anneal. The time-temperature conditions for this process have been determined by sheet resistivity studies.3 Electrical profiles of implanted phosphorus ions which have been determined by a differential sheet conductivity technique are based on the assumption that the carrier mobilities and activation energies for ionization are the same as in bulk silicon. These assumptions have been substantiated experimentally by measurement of Hall constants and resistivities of these implanted structures and the results are presented herein. After establishing the bulk property equivalence of the annealed layers, a more detailed examination of the annealing process was undertaken. The sheet resistivity technique initially used to determine anneal conditions has been broadened to include Hall constants and mobility behavior with anneal conditions. PROCEDURE The three groups of samples prepared for Hall measurements were implanted with mass-separated beams of boron, aluminum, and phosphorus ions. Ion concentrations are equivalent surface concentration and they have been determined from beam current measurements during implantation. Implant conditions for the samples are shown in Table I. In all cases, the samples had previously been angle-lapped on one edge and the junction delineated with an HF-copper sulfate solution. The surfaces of the implanted regions of the samples were exposed to the delineating solution and in the case of the "n"-type phosphorus-implanted areas it was later discovered that a finite amount of surface could be etched by this solution. This is discussed in the section on results. The implanted samples were ultrasonically cut into the conventional six-probe configuration shown in Fig. l.* In the annealing studies, for which the meas- urements were taken at room temperature, the sample holder was a Bakelite jig incorporating tungsten mechanical probes. The other measurements were taken using a conventional liquid-nitrogen cryostat, in which the temperature could be varied from 77" to about 400°K. For these measurements, 10-mil aluminum dots were evaporated onto the samples and alloyed with the silicon at 530°C for 15 min. The samples were then mounted in flat-packs, and gold wires were bonded to the aluminum dots. The electrical measurements were made with either a Leeds & Northrup K-5 Potentiometer, a Keithley 147 Nanovolt Null Detector, or a Keithley 601 Electrometer. No external bias was applied to the substrate. There is an inherent self-biasing arrangement at one or the other of the current contacts (depending upon the polarity), and this suffices to limit the current flow to the implanted layer. The magnetic field was generated by an A. D. Little electromagnet. Except for occasional checks of linearity of the Hall voltage with

Jan 1, 1969

By Mary A. Barrett

The Bureau of Mines conducted a laboratory-scale investigation of grouting mixtures containing iron or aluminum to determine the existence of health or explosion hazards, due respectively to oxygen depletion or hydrogen emission. Mixtures containing iron created an oxygen deficiency in less than 24 hours and released small amounts of hydrogen; a health hazard could occur but only under extremely unfavorable conditions. Mixtures containing aluminum released little hydrogen and consumed little oxygen; however, if improper on-site mixing yielded high local metallic aluminum concentrations, enough hydrogen might be released to produce an explosive atmosphere in a confined space.

Jan 1, 1969

By David J. T. Carson

"The metalliferous deposits of Vancouver Island have generally been assigned to the Mesozoic ""Coast Range Orogeny."" However, a metallogenic study by the writer has revealed that several important classes are early or middle Tertiary. Included are porphyry coppers, and gold-quartz, arsenic and copper-arsenic veins.The porphyry coppers and many gold-quartz veins are within and adjacent to Oligocene-Eocene quartz diorite intrusive complexes. Arsenic and copper-arsenic veins have a close spatial relationship to sills and laccoliths of Oligocene dacite porphyry which intrude the late Cretaceous Nanaimo Group.Other deposits of demonstrable Tertiary age include a molybdenum stockwork related to a relatively potassic Eocene plug and a few small copper-skarn occurrences. Some copper stockworks and a mercury deposit are probably also Tertiary.The copper deposits of previously recognized Tertiary age are those of the Sooke area that occur in Eocene basalts and Oligocene gabbros."

Jan 1, 1969

By H. I. Aaronson, C. Laird

Cold rolling by 50 pct a A1-4 pct Cu alloy containing many 0&apos; plates has been found to accelerate markedly the transformation of 8&apos; to 0 upon further aging. Although the basic mechanism of this transformation remains unchanged by plastic deformation, the nuclea-tion kinetics of 8 become appreciably more rapid and also less dependent upon temperature. Particularly at lower aging temperatures, rounded idiomorphs replace several faceted rnorphologfes. The rates of growth of 9 idiomorphs in deformed specimens aged at 300°C are appreciably more rapid than simple volume diffusion control allows. This observation is shown to be explained by an excess vacancy, rather than by a dislocation Piping mechanism of growth. ThE rather complex phenomenology of the 8&apos; —8 transformation in Al-Cu alloys has been recently elucidated in considerable detail by means of transmission electron microscopy.&apos;-4 This technique was also employed in the present investigation in order to examine the effects of plastic deformation upon the transformation of 8&apos; to 8. The mechanism of the transformation in undeformed Al-Cu alloys has been established as the following sequence of events.1"4 The first step is the nucleation of 9 at (Y:8&apos; boundaries. Nucleation of a 0 crystal takes place, however, at only a very small proportion of the 8&apos; plates present. Each 0 crystal simultaneously consumes the host 8&apos; plate and the a! in the immediate vicinity, with growth into a being the rate-controlling process. The remaining 8&apos; plates are then dissolved as they fall under the concentration shadow of the growing 8 crystals. The evidence on the effects of plastic deformation upon these processes is intriguing, but much less detailed. The careful X-ray studies of Graf and Guinier have shown that the aging times required to form detectable amounts of 8&apos; and 8 are reduced by prior cold working. Thomas and Nutting confirmed these results by replication electron microscopy. Nile-shwar,* on the other hand, reported that creep deformation decreases the rate of formation of 0. While this difference may have been caused by the use of concurrent rather than successive deformation and ag- ing, the X-ray technique which he used was able to monitor only the 0 phase. It is thus possible that the times needed to form 8&apos; were increased moreg than the kinetics of 8&apos; — 8 transformation were accelerated. At 90 pct deformation by cold rolling, Graf and Guinier found that the usual 0&apos; —0 8 sequence is reversed: 0 forms first. von Heimendahl 10 confirmed this result with transmission electron microscopy. Pollard and Nutting, 11 and more recently Driver and Barrand, 9 having used the same technique, report that 9 also forms first during creep deformation. In the present study, the maximum amount of deformation was limited to 50 pct reduction by cold rolling in order to insure that 8 formed principally by the decomposition of . I) EXPERIMENTAL PROCEDURES This investigation was conducted on an Al- 3.93 pct Cu alloy, prepared as previously described. 4 Morphological and crystallographic effects of plastic deformation were studied in specimens annealed 6 hr at 548°C, quenched, and then aged for either 3 or 8 hr at 250°C to form large numbers of 0&apos; plates. After cold rolling to a 50 pct reduction in thickness, the

Jan 1, 1969