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By W. R. Strickler, P. Hazebroek, M. Prats

The pressure and production behavior of a homogeneous cylindrical reservoir producing a single fluid through a centrally located vertical fracture of limited lateral extent was determined by using mathematical methods to solve the appropriate differential equation. It is assumed that there is no pressure drop within the fracture — that is, that the fracture capacity is infinite. It was found that the production-rate decline of such a reservoir is constant (except for very early times) when the flowing bottom-hole pressure remains constant. The production-rate decline increases as the fracture length increases. Thus, the lateral extent of fractures can be determined from the production-rate declines before and after fracturing or from the decline rate after fracturing when the properties of the formation and fluids are known. The production behavior over most of the productive life of such a fractured reservoir can be represented by an equivalent radial-flow reservoir of equal volume. The effective well radius of this equivalent reservoir is equal to one-fourth the total fracture length (within 7 per cent); the outer radius of this equivalent reservoir is very nearly equal (within 3.5 per cent) to that of the drainage radius of the fractured well. The effective well radius of a reservoir producing at semisteady state is also very nearly equal to one-fourth the total fracture length. It thus appears that the behavior of vertically fractured reservoirs can be interpreted in terms of simple radial-flow reservoirs of large wellbore. INTRODUCTION An earlier report1 has considered the effect of a vertical fracture on a reservoir producing an incompressible fluid. That investigation of the fractured reservoir producing an incompressible fluid was started because of its simplicity. Thus, pertinent behavior of fractured reservoirs was obtained at an early date, while experience was being gained of value in the solution of more complicated fracture problems. One of these more complicated problems, and the one discussed in this report, considers the effect of a compressible fluid (instead of incompressible fluids) on the production behavior of a fractured reservoir. In the incompressible-fluid work mentioned, it was shown that the production rate after fracturing could be described exactly by an effective well radius equal to one-fourth the fracture length whenever the pressure drop in the fracture was negligible. Because of the simplification in interpretation, it is a matter of much interest to determine whether the production behavior of reservoirs producing a compressible liquid could be described in terms of an effective well radius which remains essentially constant over the producing life of the field. The details of the mathematical investigation are given in the Appendixes. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The reservoir has an impermeable circular cylindrical outer boundary of radius re. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below the producing layer (reservoir). It is assumed that there is no pressure drop in the fracture due to fluid flow. Fig. 1 indicates the general three-dimensional geometry of the fractured reservoir just described. When gravity effects are neglected, the flow behavior in the reservoir is independent of the vertical position in the oil sand. Thus, the flow behavior in the fractured reservoir is described by the two-dimensional flow behavior in a horizontal cross-section of the reservoir, such as the one shown in Fig. 2. Production is due to the expan-

By A. W. Schlechten, C. M. Hsiao

The apparent vapor pressures of a number of metal sulphides were determined by measuring their rate of weight loss when they were heated under vacuum. The calculated pressures are due in some instances to the volatility of the sulphide and in others to the decomposition pressure. FIE direct reduction of metallic sulphides, as in the precipitation method for lead or antimony, is not a widely used process today. However, it might be employed for the production of a number of metals if the operation were carried out under reduced pressures. Two general procedures are possible; the reducing agent could form a stable nonvolatile sulphide from which the valuable metal could be removed by volatilization or liquation. The other approach would be to choose a reducing agent which would form a sulphide that could be volatilized away from the valuable metal. A vacuum operation would serve to protect the sulphides and metals from oxidation and would increase the evaporation rates. A related process is the separation of metallic sulphides by selective volatilization either at atmospheric pressure or under vacuum. This procedure is already used commercially for the elimination of lead and cadmium as PbS and CdS from zinc calcines; it might well have other applications. To predict such processes it is necessary to know the relative volatilities of the metallic sulphides and to know whether they volatilize as sulphides or whether the predominant weight loss is due to decomposition. Such data would also be of value in studying problems such as the use of sulphides for refractories, as described by Brewer,] or in the evaluation of the theory of ore deposition from the vapor state, as proposed by Brown.' Qualitative statements concerning the volatility of metallic sulphides can be found frequently in the literature and are well summarized by Mellor, but accurate determinations of rates of evaporation or vapor pressures are very scarce. Kelly" lists vapor pressure data only for PbS; his reference being to the work of Schenck and Albers,4 who measured the vapor pressure of PbS by a dynamic method between 850" and 995°C. More recently Veselovskii5 has determined the vapor pressures of the sulphides of antimony, lead, cadmium, and zinc at temperatures ranging from 360" to 1000°C using Knudsen's method. A second Russian worker, Pogorelyi,6 determined the vapor pressures of CdS and ZnS at temperatures from 900" to 1250°C. The results obtained by these workers are shown in subsequent graphs in comparison with the data of this paper. Brewer and coworkers1 have studied some of the metallic sulphides to determine their suitability as refractories in vacuum. Veselovskii's determinations on PbS checked well with those of Schenck and Albers, and his determinations of CdS check almost exactly with Pogo-relyi. For the vapor pressure of ZnS the data of Veselovskii and that of Pogorelyi are in fair agreement, as shown in Fig. 1, but it should be pointed out that Lumsden7 has discovered that the equation given by Veselovskii for the vapor pressure of ZnS: - 14,200 log P9.495 is in error by a factor of ten when compared to the experimental data. In contrast with the scarcity of data on vapor pressures, the decomposition pressures of many metal sulphides have been determined and are summarized by Smithells.8 Theoretical Considerations The experiments described in this paper consisted of determinations of the rate of weight loss of certain metallic sulphides under very low pressures at different temperatures. These data plus observation and analyses of the products reveal the mechanism of the weight loss and also provide a basis for the calculation of the vapor pressure or apparent vapor pressures of the sulphides.

Jan 1, 1953

By G. W. Doepel, W. P. Sibley

A three-dimensional, multilayer, mathematical model has been developed for predicting performance by mis-c.ible displacement. Areal and vertical coverage, total gas-oil ratio, propane-oil ratio and oil-recovery factor for the multilayer system are computed as functions of hydrocarbon pore volumes of solvent injected. The technique has been programed for use on the IBM-7090 digital computer and was used in calculating perfortnance for continuous miscible displacement of a five-spot, 50-layer .system. Results reported are based on the use of published laboratory data for a single, uniform five-spot layer. However, the technique is sufficiently generalized to calculate performance of any system of layers of any pattern configuration and mobility ratio, provided data are available to describe perfortilance of a single layer. The technique has also been adapted for predicting oil recovery resulting from various gas-driven slug sizes. The results presented for both continuous and slug-type injection show, that permeability variation has 0 significant effect on oil recovery but that solvent composition, within the range studied, has a lesser effect on oil recovery. INTRODUCTION Experience from many of the miscible-phase displacement projects currently in operation indicates that the injected solvent flows preferentially through the more permeable zones in the reservoir. This preferential solvent flow in the high-permeability streaks results in a reduction of vertical coverage (C,) and an attendant decrease in oil recovery. The multilayer technique presented in this paper uses areal coverage (C.,) data for a single layer from the literature and from laboratory measurements of displacement efficiency (herein referred to as microscopic coverage, C,,) to calculate areal coverage (C,) and vertical coverage (C,) for the multilayer system. Oil recovery for the multilayer system is obtained as the product of (Ca) (Cm) (Cv). It is assumed that C, in a single layer is 100 per cent; therefore, (C,) (Cm) is a measure of oil recovery from that layer. Data presented in the literature for a single layer generally deal only with areal coverage and/or microscopic coverage —but seldom specifically with oil recovery. Nevertheless, this technique is flexible in that either Ca and C,, of an individual layer or a direct measurement of oil recovery for the layer may be used. In developing this technique, the problem arose concerning a method of determining the relative amounts of solvent that will enter each layer during any increment of solvent injected. To solve the problem, a dimensionless equation was derived for expressing solvent injected into each layer as a fraction of total injection. A finite-difference method was applied in integrating the equation to determine oil recovery for the system of layers as a function of pore volumes injected. The technique subsequently was programed for solution on a digital computer. The method was applied to predict performance of a deep California reservoir under continuous miscible displacement and has been extended for calculating oil recovery as a function of slug size for gas-driven slug injection. The technique may be applied to any petroleum reservoir that can be adequately represented as a layered system, by considering permeability variation,1-3 permeability range and average permeability. Each layer is then assigned its appropriate permeability, porosity and hydrocarbon saturation. RESERVOIR VOLUME CONTACTED BY SOLVENT It has been recognized for some time that high microscopic coverage (C,) can be obtained by injecting a miscible agent, such as propane, into an oil reservoir. These high values of C,,, have been demonstrated in the laboratory and are normally between 80 and 100 per cent, depending on solvent and reservoir oil composition as well as on reservoir temperature and pressure. In miscible-phase displacement, because there is no interface between solvent and oil, effective permeability to solvent is the same as that to oil. (This assumes that oil saturation has not changed and that water is immobile.) Consequently, mobility ratio (M) simply reduces to that of viscosity ratio . Perrine4 and Habermann5 have shown that large

By Herman Dykstra, Irving Fatt

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.' Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George' showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille's Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell's equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille's Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy's Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy's Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI' By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951

By A. G. Metcalfe, A. Siede

The hardening of annealed copper during fatigue testing appears to be independent of the applied stress and to occur largely within the first 4000 cycles. Copper hardened by fatigue is more resistant to annealing than copper hardened by static means, and softens by a multistage process. Creep studies at 300°C show that copper hardened by fatigue also has greater resistance to creep than statically hardened copper. Some theoretical explanations are discussed. RECENT interest in the behavior of metals subjected to fatigue stems from observations of phenomena which could not be explained by current theories of the structure of metals. In 1953 Bullen et al.l showed that the hardening caused by fatigue at low stresses did not cause severe bending of the lattice as did hardening by static methods. This was later confirmed by Wood, 'and Broom and Ham.3 Clarebrough et al4 showed that as the stress level used in fatigue hardening was increased, bending of the lattice was introduced, eventually approaching that of metals deformed by conventional cold-working methods. The type of hardening introduced by fatigue has other interesting characteristics. Kemsley5 showed that copper fractured by fatigue at low stresses resisted annealing as compared to copper hardened an equal amount by static means. The work of Clarebrough etal, shows that the manner of energy release during annealing differs for fatigue-hardened and statically hardened metal in both magnitude and temperature range of release. In addition to hardening of the lattice, fatigue has been shown to cause softening in materials previously hardened by static methods,5 and also in age-hardened alloys.7 The superposition of a small fatigue stress on the static loading of high-temperature alloys has been shown to increase their resistance to creep.' The present work was an attempt to determine the relationship between fatigue hardening, resistance to annealing, and the creep properties of pure copper. EXPERIMENTAL PROGRAM The program described here was designed to answer three questions: 1) Can stress-cycle combinations well below the failure values give significant increases in hardness? 2) Does hardening, under different stress-cycle combinations, give increase resistance to annealing? And if so— 3) Does superior resistance to annealing confer superior creep properties over statically hardened material? Three-quarter hard OFHC copper was annealed in vacuo at 550°C for 1 hr to produce a strain-free material having a fine grain size and uniform hardness. (The standard deviation of the mean hardness of the annealed samples was less than + 1.9 Dpn). Annealing was performed after machining the fatigue specimens so as to avoid work-hardened surfaces. Jigs were used to avoid distortion. The fatigue properties of the annealed copper were determined using an accurately aligned Baldwin-Sonntag SF1-U machine operating at 1800 cycles per min. This limited the minimum number of cycles which could be examined to about 4000 stress reversals. Since failure resulted in specimen damage, hardness increase with number of cycles was measured by testing specimens fatigued to different fractions of the failure values. The results are shown in Fig. 1, and are superimposed on the S-N curve of the copper in Fig. 2. The resistance to annealing of fatigue-hardened material was compared to that of material hardened by uniaxial tensile straining. Specimens hardened to equal values by both methods were progressively annealed for 1 hr at temperature in vacuo. After each annealing treatment the hardness was measured using a Leitz Durimet hardness tester with a 500-g load. At least five tests were made for each hardness determination. The standard deviation for individual specimens varied from 0.26 to 1.48 hardness points. The results are shown in Figs. 3 to 5. The discontinuous nature of the annealing process has been brought out by drawing idealized curves through the data points. This can be justified by the consistency of the results as well as by general agreement with results of Kemsley.5 The creep resistance of fatigue-hardened and

Jan 1, 1960

By Harvey T. Kennedy, Erasmo T. Guerrero

In this investigation, the effects of the surface tension of brine and the interfacial tension between oil and brine on the recovery of oil by water flooding of Woodbine sand were studied. Variation of the surface forces was obtained by the addition of small amounts of commercially available chemicals, which did not appreciably change the surface tension of the oil. Fourteen surface-active agents, which were found to be effective in lowering the surface and interfacial tensions, were further investigated to determine the extent of their adsorption by the Woodbine Sand cores. It was found that adsorption was sufficient in all cases to prevent any substantial concentration of chemical at the flood front. The flow system was, therefore, brought to equilibrium with definite concentrations in the flood water by circulation before each test. The data thus have no relation to the results obtainable by using the chemicals in full-scale water floods, but should be helpful in predicting the performance of surface-active chemicals which are not lost by adsorption, if such can be found. Flow tests were made on various concentrations 01 six chemicals selected from the 14 investigated for surface activity and adsorption, with and without the presence of gas in the core. It was found that lowering the interfacial tension had a tendency toward reducing the recovery of oil and that the reduction of the surface tension of the brine had little or no effect. A substantial beneficial effect, however, resulted from the presence of gas in the cores. INTRODUCTION The movement and distribution of crude oil in a porous medium are governed by such factors as surfacc and interfacial tensions, viscosity of the oil, pore size configuration, and wetting characteristics of the medium. The knowledge of the part played by each of these factors is limited. If the oil is assumed to be distributed in droplets whose movement is restricted only by the pore openings, the following equation may be applied: ?P= 2r(1/r1-1/r2) .......(1) In this equation ?P is the pressure drop necessary to force an oil droplet through the construction, r is the oil-brine interfacial tension, r1 is the radius of curvature at the forward and smaller end of the deformed droplet, and r2 is the larger radius. This equation neglects the effects of viscosity, as a static or near static condition is assumed. It would apply equally well for a bubble of gas in liquid if r were taken as the surface tension of the liquid. This relation shows that droplets can be more easily displaced if the interfacial tension is decreased. The displacement of oil from the surface of a sand particle may also be considered from the basis of selective wetting assuming that the oil droplets are smaller than the pore constructions and that the sand surfaces may be considered as planes. A relation of the forces involved can be derived from Dupre's equation to give: Wos = row (1 +Cos?)........(2) where Wos = Work of adhesion between the sand and the oil row = Oil-water interfacial tension 0 = Contact angle ros = Oil-solid interfacial tension This equation would indicate that the displacement of oil from a sand surface is more readily obtained when the water-oil interfacial tension is reduced provided the contact angle remains constant. Evidently. however, the values of Cos 0 may vary along with the water-oil interfacial tension due to changes in the other surfaces of the system. The above theoretical considerations suggest that perhaps even the static behavior of a dispersed oil phase in a porous medium is considerably more complex than may be inferred by the simple systems

Jan 1, 1955

By S. S. Marsden, S. H. Raza

An experimental study of the flow of line-textured. aqueous foams through Pyrex tubes is described. The foams range in quality F (ratio of gas volume to total volume) from 0.70 to 0.96 and behave like pseudoplastic fluids. At lower flow rates they exhibit laminar flow ad have apparent viscosities which increase with quality, and which cover a range of 15 cp to 255 poise for tubes of 0.25- to 1.50-mm radius rj. At higher flow rates a plug-like type of flow is developed, the extent of which increases with both T and ri. When the same foams flow through either open or packed Pyrex tubes, remarkably high streaming potentials ?E are often generated. These can easily reach 50v if nonionic foaming agents are used, but are at least an order of magnitude less for ionic foaming agents. A linear relationship between ?E and the pressure differential ?p is observed; this usually extrapolates to positive values of ?p at ?E of zero. The slope of the line increases with both F and ri. An equation was derived to describe the streaming potential of non- Newtonian fluids in circular tubes and was used to correlate experimental results. The calculated < potentials are of the right order of magnitude. INTRODUCTION Foams are both unusual and inniguing in their physical properties, and have been the subject of many scientific studies. However, present knowledge of foams is still fragmentary, specific and often contradictory. Apparent viscosity of foam is the physical property of greatest interest to both rheo1ogists and engineers. sibreel reported that the apparent viscosity decreased with increasing shear rate in a manner similar to some non-Newtonian fluids. Penny and Blackman2 reported that fire-fighting foams had both a limiting shear stress and a tensile yield stress. There is little doubt that some foams at least behave like non-Newtonian fluids, and have apparent viscosities considerably higher than those of either constituent phase. The high apparent viscosity of foam with its concomittant effect on mobility ratio and sweep efficiency no doubt prompted several attempts by research groups to use foam as a displacing agent in porous media. Based on recent experience, most of these groups probably succeeded in completely blocking fluid flow in the porous media and then abandoned their efforts. Two groups apparently found the successful combination of experimental parameters at about the same time.3,7 Others have recently added to our knowledge of foam flow in porous media and its use as a displacing agent.8-13 An experimental problem encountered by Fried3 was a transient blockage of foam flow in porous media when distilled water was used to prepare the foam-producing solution. Fried surmised that this was due to an electrokinetic effect and he eliminated it by using electrolytes in preparing foaming solutions. He also measured the streaming potential of a number of foams in capillary tubes which he found to be appreciably higher than those obtained when the constituent liquid flowed under comparable conditions. This paper presents results of a more comprehensive study of the streaming potential generated by aqueous foam flowing in both open and packed Pyrex tubes. It also adds to knowledge of the rheology of these foams as deduced from their flow behavior in open tubes. APPARATUS AND PROCEDURE A diagram of the apparatus used is shown in Fig. 1. Details of its construction, testing and use are described elsewhere.14 Careful selection of materials, extreme cleanliness and rather elaborate electrical insulation and shielding were necessary to obtain reproducible results (±5 percent). Both streaming potential and streaming current were measured with an electrometer. The design of the foam generator developed for this work is novel (Fig. 2). It will produce uniform fine-textured foams at pressures sufficiently

By Irving Fatt, Herman Dykstra

Relative wetting phase permeabilities calculated from capillary pressure-saturation data are compared with measured relative permeability data. The equation relating relative permeability to capillary pressure-saturation data is derived by assuming that a porous medium is analogous to a bundle of capillary tubes. The equation includes a term to correct for the difference between fluid path length and length of core. Relative oil permeability data in the water-oil-gas system are presented, and it is shown that if the water is considered part of he rock matrix, the relative oil permeability curve is typical of a wetting phase relative permeability curve. Apparatus for measuring two and three-phase relative permeabilities are described. INTRODUCTION The difficulty in measuring relative permeability of cores has made it desirable to have a correlation between relative permeability and some more easily measured property of porous media. Such an easily measured property is the capillary preisure-saturation relation. In the past there has been a tendency to separate the capillary pressure concept from the very complex pore geometry and to consider that the capillary pressure-saturation curve give? only some characteristic distribution of interfacial curvature between two fluids.&apos; Recently, however, it has been realized that if capillary pressure data are to yield information concerning pore size distribution2 and fluid flow in porous media. the pore must be assumed to have a simple shape such as a cylinder or a sphere. Childs and George&apos; showed that relative water permeability could be calculated from the capillary pressure-water saturation curve by assuming that the pores are cylinders in which the fluid flowing obeys Poiseuille&apos;s Law, and that the capillary preisure curve indicated the size and number of pores. Purcell5 derived an equation relating the permeability of a porous medium to the capillary pressure curve by assuming the porous medium to he analogous to a bundle of capillary tubes. Gates and Lietz6 calculated relative permeability by an equa-tion derived from Purcell&apos;s equation. In this paper an equation is derived giving the relative water permeability as a function of water saturation by as-sulning that the core sample can be represented by a bundle of capillary tubes in which the fluid path length is not the same as the bulk length, and in which the fluid path length varies with saturation. THEORY For a bundle of N capillary tubes the flow through dN tubes will be dQ = qav dN ..........(1) where Q is the total flow rate through all the tubes and q., is the aberage flow rate through the tubes in the interval dN. If the interval dN is made small the average flow rate through a tube in the interval dN is given by Poiseuille&apos;s Law, 8 nl where ?P is the pressure drop across the tube of length 1 and radius r, and µ is the viscosity of the fluid. Substituting for qav in Equation (1), dQ =pr4 ? P/8µl dN.........(3) Darcy&apos;s Law for linear flow of an incompressible fluid in a porous medium is Q = KA?P/µL...........(4) where K is the permeability and ?P is the pressure drop across a bundle of tubes which has replaced the porous medium of length L and cross-sectional area A. Differentiating Darcy&apos;s Law with A, ?P, µ, and L constant, dQ = A?P/µL dK.........(5) Equating (3) and (5) gives dK------------dN.........(6) 8Al If the pores are assumed to be cylinders dV =pr2ldN..........(7) where V is the volume of flowing fluid in the pores. Substituting for dN in Equation (6) gives dK = —dV..........(8) 8AI&apos; By definition the saturation, S, of the core is v v S =V/Vp..........(9) Vv -PAL

Jan 1, 1951

By John P. Hager, Igor A. Wilkomirsky

The thermodynamic properties of the Pb-Ag system have been determined between 775° and 950°C by the cell: Electrotransport measurements on silica-saturated PbO-SiO2 melts established that the conduction was entirely ionic and that lead is present only in the divalent state. The activities of lead and silver exhibit Positive deviations from ideal behavior. In dilute solutions the activities of lead and silver follow Henry&apos;s law. The values obtained for yhb and yig at 1200°K are 1.49 and 1.69, respectively. Determination of a portion of the liquidus curve agrees well with the established phase diagram. provides an accurate means for the thermodynamic study of liquid alloy systems. However, Wagner and wernerl have shown that cells of type I are limited to alloy systems for which the reaction at the alloy-electrolyte interface will be extremely small. The traditional electrolyte for cells of type I has been a low melting point mixture of group IA chlorides, to which a small amount of the compound ACIZa has been added. However, the choice of a chloride electrolyte may not always be practical, in that the Gibbs free energies of formation of the compounds ACIZ, and BCIZb may not be sufficiently different to minimize Reaction [I]. On the other hand, the Gibbs free energies of formation of the oxides of metals A and B may be sufficiently different to minimize Reaction [I]. In this case, the use of molten oxide electrolyte would be clearly advantageous. In the present study, the thermodynamic properties of the Pb-Ag system have been investigated using the cell: Previous galvanic cell studies on the Pb-Ag system2&apos;= are not reliable due to the displacement reaction between the alloys and the chloride electrolyte. Wagner and ~erner,&apos; using Laitinen and Liu&apos;s&apos; value at 450°C for the standard electrode potential of Reaction 111, have estimated the percent error in the activity of lead bPb) when using a chloride electrolyte. At 1000°C the error for xpb = 0.10 is 12 pct. Taking the Gibbs free energies of formation for PbClz and Ag cI,&apos; and the equations of Wagner and Werner,&apos; the error in apb at 1000°C and Xpb =0.10 was calculated to be 140 pct. However, using the Gibbs free energies of formation for Pb O&apos; and an estimated value for Ag 20, the error in apb when using a molten oxide electrolyte at 1000°C was estimated to be less than 1 pct for The virtual reaction of cell I1 for the passage of n Faradays of positive electricity from left to right in the cell is: where 5 is the Faraday equivalent (23,063 cal per v equivalent), E is the electromotive force of the cell in volts, and n is the number of Faradays of electricity required for the transfer of 1 g-atom of lead through the cell. The value of n should be equal to 2 since lead is generally divalent in oxide melts. However, the presence of either tetravalent lead ions or electronic conductivity through the molten oxide electrolyte will result in a value of n greater than 2. Bockris, Kitchener, and Davies&apos; have determined the amount of ionic conductance in a liquid PbO-SiO2 mixture (xPbO= 0.50) at 920°C by measurement of the volumes of CO and C& evolved at a carbon anode during electrolysis. From their data a value of 2.13 * 0.16 was calculated for n. Although their measurements indicate the possible presence of multivalent lead ions and/or electronic conductivity, their measurements were not at silica saturation and no definite conclusions can be drawn. However, as a result of the electrotransport measurements described in the next section the ;due of n can be taken as equal to 2.

Jan 1, 1969

By A. M. Gaudin

Activation of sphalerite with silver ions results from the exchange of two Ag ions for one Zn ion in the sphalerite lattice. The exchange is proportional to the logarithm of time and proceeds until either of the reactants is consumed. Sodium cyanide prevents the activation of sphalerite by controlling the ratio [Zn++]/[Ag+]&apos; in solution. If sphalerite has already been activated with excess silver, cyanide ions can deactivate sphalerite provided oxygen is present. SOLUBLE: silver salts are effective activators for flotation of sphalerite with potassium ethyl xan-thate as collector.* Since sphalerite takes up large quantities of silver ions rapidly,2-4 investigation of this system appeared fruitful for studying the mechanism of sphalerite activation and deactivation. Experimental data presented here comprise studies of the mechanism and rates of activation and deactivation of sphalerite with silver and cyanide ions. A 20-lb sample of sphalerite from Ottawa County, Oklahoma, was handpicked, crushed, screened, hy-drosized to produce a 65/100-mesh fraction, and purified by electrostatic separation. The sphalerite was then leached with benzene and absolute ethyl alcohol to remove possible organic contaminants and with 0.1 M NaCN to remove any copper that might have been picked up during screening. The benzene had been specially purified by grinding with fine sphalerite for 12 hr to remove trace impurities that might have had a specific affinity for sphalerite. Ii&apos;inally, the mineral was washed, dried in flowing nitrogen, and stored in large ground-glass stoppered weighing bottles under a small nitrogen pressure. The specific surface of two samples from the 65/100-mesh sphalerite stock, measured by krypton gas adsorption," was 420 cm2 per g. Compared with spheres of the same size and specific gravity, the prepared mineral had five times as much surface. Results of a wet chemical analysis and of a spectro-graphic study are given in Table I. Manganese, nickel, tin, indium, thallium, cobalt, and magnesium were not detected spectrographically. All solutions were preparid by -adding reagent-grade chemicals to conductivitv water. which had been previously saturated with the desired gases. Nitrogen and oxygen were purified, but no attempt was made to purify the laboratory air. Radioanalysis was carried out with prepurified Ag110 tracer obtained from the Oak Ridge National Laboratory. The complete decay scheme for Ae is complex. Its primary emissions are 0.09 and 0.55 mev ß rays and 1.48 mev y raysB and its half-life is believed to be 270 days. In preparation of solutions of AgNO3, the amount of Ag110 added was negligible compared to that of the inert silver. Abstraction of silver from solution by sphalerite was measured after agitation of 1.5 g sphalerite with 20 ml of solution in 50-ml pyrex flasks. All sample preparations were carried out in a dry box so that the proper atmosphere could be maintained. After the mineral had been agitated in the silver nitrate solution, an aliquot of the solution and a sample of the wet mineral were transferred to separate counting vials and weighed. The solid sample was dried and re-weighed and the activity in both vials measured by means of a scintillation counter. With scintillation counting it is possible to count y radiation from the solid and liquid, a distinct advantage over the older ß-ray counting techdiques.4 All measurements of silver activity were made using a sodium-iodide well-type scintillation counter. The amount of zinc in solution was measured colorimet-rically by the monocolor method of Sandell.7 Activation Studies Exchange Between Zinc Ions and Silver Ions During Activation: The increase of Zn++ in solution during activation with Ag+ is shown in Table 11. These data indicate a replacement of one Zn++ by two Ag+. Analysis of a separate two-month agitation test indicated that the replacement of Zn++ by Ag+ was, as expected, in the molar ratio of 2.0.

Jan 1, 1958

By G. R. Wilms

A study has been made of the structural changes in polycrystalline high purity aluminum during the tertiary stage of creep under conditions of constant tensile load. It appears that there is no basic modification in the particular mechanism of deformation that characterized the preceding secondary stage of creep, but that the changes in crystalline structure produced during the tertiary stage are only a consequence and not a cause of the accelerated strain. Intercrystalline fissures were observed on entry into the tertiary stage, and these might supplement the accelerated rate of strain owing to local stress concentrations. There is evidence that the formation of these fissures may be associated with the presence of surface imperfections, and it is suggested that a more generalized treatment of the results may explain certain creep characteristics of commercial alloys. IN previous work&apos;-4 a study was made of the changes produced when specimens of annealed aluminum were deformed at various temperatures and rates of strain, especially under conditions leading to creep under constant tensile load. It was shown that, as the temperature was increased or as the rate of strain was decreased, elements of the substructure produced within the grains became coarser, and with the strain rate constant at a given temperature, their size tended to an equilibrium value. The preliminary process of the breaking down of the grains into a substructure was identified with primary creep.&apos; The subsequent equilibrium, condition was associated with secondary creep. The question then arose whether the tertiary stage corresponded to any further significant change in the substructure. The question is also of interest in view of the opinion, expressed for instance by Andrade,5 that the tertiary stage is merely an accelerated rate of strain due to the reduced area of section of a specimen under continuous tensile load, and the other opinion, as suggested by the observation by Sully, Cale, and Willoughby6 of a tertiary stage in com-pressive loading, that this third stage is a real effect in its own right. The object of this paper is to record some observations on the tertiary stage of high purity aluminum. Experimental Procedure The material was aluminum of 99.98 pct purity as previously used. The specimens had a rectangular section of l/8 x l/2 in., and extensions were measured over a 1 in. gage length. After machining to shape, the specimens were annealed to give a standard grain size of 0.2 mm and then electropolished. The general procedure involved metallographic and X-ray diffraction examination at progressive stages of elongation (marked by arrows on the curves shown in Figs. 1 and 2), the specimen being extended to fracture under constant load at a given temperature. The X-ray tests were made by the back-reflection method from a stationary specimen, using CoK radiation. The longer edge of the micrographs in the paper corresponds to the direction of applied stress. Results The previous work showed that, in the secondary stage of creep in aluminum, three basic types of structure could be developed according to the temperature and rate of strain. These were: 1—slip, which predominated at the lower temperatures and higher rates of strain and produced the finest and least perfect substructure; 2—cell structure, which superseded slip as the temperature was raised and the rate of strain decreased and which was characterized by a coarser and more perfect structure and an absence of slip lines; and 3—a stage termed "boundary microflow," which predominated at still higher temperatures and lower rates of strain when the cell size had increased and become comparable

Jan 1, 1955

By J. D. Doherty

That America&apos;s great coal deposits eventually will be our principal source of liquid as well as solid fuels is generally accepted. Moreover, the day when synthetic oil from coal will begin to supplement our petroleum supplies does not appear to be far off. The American petroleum industry has not spared effort or expenditure in its attempt to keep pace with the demand for oil, and recent production has exceeded expectations. However, the rapidly rising demand for liquid fuels plus the increasing difficulty of finding and developing the new oil needed even to maintain present production rates make it highly unlikely that oil from domestic wells can fully meet future oil requirements. Therefore, it appears that one or more of the following courses must be followed: 1. Curtail oil consumption. 2. Incr ase imports. 3. Develop new sources such as synthetic liquid fuels. All three courses may well be needed, as it is doubtful that any one of the three alternatives alone can satisfactorily solve the problem indicated by the prevailing trend in demand for oil. Curtailment of oil consumption is not a constructive policy, except where oil is being wasted or coal can be readily substituted as in stationary steam plants. Reduced oil supplies for most uses will curb our economic advancement and, in addition to inconveniencing consumers, will have a pronounced adverse effect on American industry. The oil-burner-manufacturing industry already has been dealt a hard blow. Shipments in the first 5 months of 1948 decreased 70 pct from those in the same period in 1947.1 The effect of a similar cut in the automobile industry can be imagined. A severe prolonged shortage of gasoline could seriously disturb our present economic well-being. It might be pointed out also that even the prospect of a shortage or lack of assurance for the future can discourage buyers of equipment, as occurred in the case of oil burners. An increase in our imports of oil seems to be a necessary expedient for the immediate future. Its advantages are that it will require a minimum of manpower and steel in a time of critical shortages and will conserve domestic reserves. Any major dependence upon foreign sources for our oil supplies should be avoided, however. Other nations are increasing their oil consumption more rapidly percentagewise than the United States and eventually will compete with us for the not unlimited world supplies. In peacetime, foreign countries might restrict ship- ments of oil to this country or impose exhorbitant prices. In the event of war, there is serious danger that such sources would be cut off, and American-developed oil fields overseas might even be used against us. Although synthetic fuels cannot relieve any oil shortage that might develop within the next year or two, an immediate start toward a substantial synthetics industry to supplement petroleum not only could help relieve shortages several years hence but also would help establish the much needed "know-how" for large-scale production. By assuring ample future supplies, such a start would permit sound planning by industries dependent upon oil and maintain or restore the confidence of prospective customers for oil-con-suming equipment. If it is agreed that domestic production of crude oil cannot be expected to meet future domestic demands, that oil rationing in general is undesirable. and that too great dependence on foreign oil should be avoided—and the weight of the evidence supports such conclusions—it is inescapable that commercial synthetic fuel production should be developed to supplement domestic petroleum supplies, which, of course, will furnish the bulk of our requirements for yean to come. Sources of Synthetic Oil The three principal sources of synthetic oil are natural gas, oil shale, and coal. A commercial plant using natural gas is under construction, and expansion of this industry is expected.

Jan 1, 1950

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,&apos; Mc Quillan,&apos; Van Thyne et dl.,&apos; and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger&apos; discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95&apos; *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By F. W. Jessen, N. Mungan

The plastic flow characteristics of clay water suspensions were first recognized by Binghaml in 1916 and further studied by Ambrose and Loomis&apos; in 1931-1932. Many physical and chemical properties of clay suspensions are deeply influenced by particle size distribution as well as by the exchange cation. Separation of a number of fractions is particularly helpful in making a detailed study of a suspension. A limited amount of work has been conducted on the effects of particle size on specific properties of mud drilling fluids. A knowledge of particle size distribution is essential for a better understanding of fundamental properties of clay suspensions, particularly viscosity and gel strength. The purpose of this investigation was to study the effect of particle size on the viscosity and gel properties of clay suspensions and to determine any changes in mineral composition accompanying variation in size. EXPERIMENTAL PROCEDURE Numerous methods may be used to fractionate a poly-dispersed clay suspension into nearly mono-dispersed systems. Particles larger than 44 micron (325-mesh) may be obtained by wet screening. For sizes from 44 to 1 micron, the fractionation may be accomplished by sedimentation, elutriation plus microscopy,&apos; or turbidimetry.6 When dealing with systems which contain a major portion of particles below l-mi-cron size, slit ultramicroscopy,7 centrifuge methods of Svedberg,5 eams,9 and McBain,l0 and X-ray methods" may be employed. The Sharples super centrifuge has been proved suitable for the economical separation of suspended particles of submicron range.12,13,14 Three-hundred and forty-five gal of 1 per cent by weight Aquagel suspension was mixed in a high-speed 5-gallon mud mixer and the suspension was allowed to stand in 5-gal glass bottles for 30 days to assure full hydration. All particles larger than 44 microns were removed by wet screening. Five fractions in the range of 44 to 1 micron were obtained by sedimentation. The Sharples super centrifuge method described by Hauser and Reed.13 Norton and Speil,14 Ha user and Lynn,15 and Hauser and Schachman,10 as employed to yield five fractions of submicron size. A super centrifuge operation chart prepared by Fancher, Oliphant, and Houssierre12 was used to determine operating conditions for the desired particle ranges. The clay suspension, after removal of all material above 1-micron size, was centrifuged. During rotation of the bowl, the particles were deposited on a thin plastic liner which fit closely inside the bowl. After passing 5 gal of suspension through the centrifuge, the liner was removed and the particles on the liner were scraped off, remixed and recentrifuged. This was repeated five times. Thus, Fractions H, I, K, and L were obtained. The finest fraction, M, remained in an approximately 0.4 per cent suspension. Water was evaporated under reduced pressure from this suspension to yield the finest particles. Results of the fractionation are included in Table 1. In order to achieve proper orientation and humidity conditions for X-ray diffraction analysis, the following procedure was employed. The dilute suspensions were placed on glass slides and allowed to dry at room temperature. This was repeated several times. Previous to measurement each sample first was placed in a water desiccator for half an hour and then allowed to stand for 15 minutes at room temperature. thus yielding an equilibrium condition of about 52 per cent relative humidity. The relative humidity of the room in which the X-ray diffraction was carried out was maintained at approximately 50 per cent so that there was no change in the spacings during the X-ray examination. Samples

By J. Weertman

It is shown that conditions suitable for the conversion of straight dislocations into helices are common in crystals hardened either through long-range dislocation interaction or by jog formation on dislocation lines. For dislocations other than screw dislocations or dislocations nearly screw in orientation, helices can be formed with the aid of core difhsion at temperatures low relative to the melting point of the material. It is assumed that, once formed, helices will degenerate into dislocation tangles. THE dislocation tangle is one major dislocation arrangement observed by the transmission electron microscope which had not been predicted previously from dislocation theory. Since first being observed, the tangle itself has become important in applied dislocation theory. The Cambridge school (P. Hirsch) bases part of its theory of work hardening upon this phenomenon.&apos; In spite of the fact that the tangle obviously is a structure of prime importance to a cold-worked crystal, until recently relatively little attention has been paid to the question of exactly why or how tangles arise. It was generally assumed at first that cross slip and perhaps jog formation will lead to tangles. However Wilsdorf and schmitz2 concluded that cross slip cannot markedly contribute to the tangles. The Wilsdorfs and Maddin3&apos;* have proposed that tangles arise by means of prismatic dislocation loops and superjogs which are produced by a precipitation of point defects. Dislocations with superjogs or which have joined with prismatic loops are themselves dislocation sources and they can produce new dislocations, a process they call "mushrooming", which then tangle with each other. There is no question that the Wilsdorfs et al. mechanism as well as the cross slip one can pro- duce tangles. However these may not be the only paths leading to tangle formation. In this paper we wish to consider another way tangles can form. Our work will be based on the theory of dislocation screw We wish to show that whenever a crystal is cold-worked there always is present a "driving force" leading to helix formation and thus to tangle formation. We do not expect to observe well-developed, regular helices in cold-worked metals. Rather we would expect that after a helix is formed random interactions with nearby dislocations will cause a well-developed helical dislocation to go over into an irregular form. A dislocation tangle is, of course, a grouping of dislocations with irregular forms. Therefore we feel that, in accounting for the formation of dislocation tangles, it is sufficient to show that many dislocations in a cold-worked crystal will take on helical form. The crucial step is helix formation. In order to have a straight dislocation assume a helical form, diffusion of vacancies, or interstitials, must occur. Our discussion of tangle formation therefore will be limited to crystals which have been deformed at temperatures ranging from about one fifth to half their absolute melting point. In this tem per a ture range appreciable core diffusion is possible. (There is no problem in explaining tangle formation at temperatures greater than half the melting point. At such temperatures dislocation climb through a bulk diffusion of point defects gives an extra degree of freedom to dislocation motion. This extra freedom of motion makes tangle formation easy.) At temperatures much below one fifth the absolute melting temperature diffusion processes are sufficiently slow that helix formation does not occur. Of course helix or tangle formation could occur in material deformed at very low tempera-tures which was subsequently warmed in order to make the thin specimen necessary for electron-microscope examination. Since within the temperature range of approximately one fifth to half the melting temperature the diffusion of point defects in the core of the dislocation is rapid, we can reasonably assume that within

Jan 1, 1963

By P. K. Weimer

Coinpletely integrated thin-film circuits inco?,porating more than 1000 active and passive elements have been fabricated reproducibly in the laboratory by evaporation of- all components. A 180-stage modified shift register comprising 540 CdSe TFT&apos;s, 360 resistovs, and 180 capacitors was deposited upon a glass substrate during one pump-down of the vacuum systeitl. Experimental units have been operated for more than 5000 hr at temperatures uP to 85°C without failure of any slages. The present pupper reviews the charvactevistics of evaporated thin-film transistors (TFT&apos;s) and discusses their application to integrnted circuils. INTEGRATED circuits most widely used today are based upon silicon technology, with the circuits formed on the surface of a block of single-crystal silicon1 or on a block of sapphire 2,3 upon which a thin layer of silicon has been deposited. Transistor patterns and interconnections are defined by photographic procedures using photoresist masking. Large groups of transistors are produced in batches which undergo many processing steps, some of which are carried out at elevated temperatures. Passive elements are formed by treatment of the semiconductor surface or are deposited by evaporation alongside the active elements. The size and complexity of the circuits are limited by defects in the devices and by the size of the available single-crystal chips. Capacitative coupling to the semiconducting substrate may also limit useful size and frequency response of the circuits. An alternative approach to integrated circuits is based upon the deposition by evaporation of all circuit components upon a noncrystalline, insulating substrate such as glass.4 Thin-film field-effect transistors,1&apos;6 known as TFT&apos;s, can be deposited in large arrays on glass or plastic substrates at the same time the associated passive elements are being deposited. Although still in the research stage the all-evaporated approach is expected to offer certain advantages for many applications. In particular, the use of thin films upon a noncrystalline substrate offers the prospect of producing complex, large-area circuits not now feasible with single-crystal silicon. Important applications of this type include memory arrays for computers and imaging devices for television. The ease with which the evaporated TFT&apos;s can be deposited may permit continuous, automated production methods not possible with high-temperature batch processing. Recent advances7&apos;8 in the fabrication of thin-film transistors have led to greatly improved reproduci-bility and life of the TFT&apos;s. Experimental circuits having over 1000 active and passive elements deposited upon a common glass substrate are currently being produced in the laboratory. The present paper reviews recent progress in the development of the TFT and in its application to integrated circuits. I) DESCRIPTION OF THE THIN-FILM FIELD-EFFECT TRANSISTOR The TFT is a field-effect transistor of the type having the control gate separated from the semiconductor by a thin insulating spacer. Although its operation resembles that of the silicon MOS transistorg its construction is based entirely on thin-film techniques. Fig. 1 shows a cross-sectional view of an evaporated TFT deposited upon a glass substrate compared with a silicon MOS transistor deposited upon single-crystal sapphire.3 The semiconductor in the TFT is a poly crystal line layer, of a material which can be readily evaporated, such as cadmium sulfide, cadmium selenide,l0 or tellurium." Silicon monoxide layers have usually served as the gate insulator, but other oxides, sulfides, and fluorides may be used. Film thicknesses range from a few hundred to a few thousand angstroms. The source, drain, and gate electrodes in the TFT are of metal. Qpical source-drain gap dimensions are 0.0003 x 0.030 in., with a gate strip whose width slightly overlaps the source and drain. The source and drain electrodes should make low impedance contacts to the semiconductor. With cadmium sulfide films, gold is a satisfactory material for underlying electrodes, while aluminum is preferable for overlying electrodes.12 Considerable variation in design of the TFT is permissible, with the electrodes being

Jan 1, 1967

By W. S. Hyler, W. L. Bruckart

The powder metallurgy and arc-cast types of wrought molybdenum stock were studied in rotating beam fatigue. Endurance ratios of unnotched specimens after 5x10 cycles were found to be 0.74 and 0.81, respectively. Fatigue notch factors (K,) of 1.36 and 2.05, respectively, were obtained on V-notched specimens having a theoretical stress-concentration factor Kt = 3.1. MOLYBDENUM and its alloys are rapidly gaining importance as engineering materials of construction for high temperature applications. AS a wrought material, molybdenum and its alloys are outstanding above 1800°F. It is necessary, however, with molybdenum to provide elevated temperature oxidation protection. This is currently being studied by a number of investigators. Thus far, there have been no published data on the fatigue behavior of molybdenum either at room temperature or at elevated temperature. The knowledge of fatigue behavior, particularly notched fatigue behavior, becomes increasingly important as the engineering importance of a material increases, especially from the design standpoint. The work described here was directed toward determination of the notched and unnotched rotating beam fatigue characteristics of molybdenum at room temperature. Also, it was desired to learn whether any difference exists between wrought molybdenum of the powder metallurgy and the are-cast types. Fabrication History of Bar Stock For this work, bar stock was procured from Climax Molybdenum Co. (are-cast type) and from Westing-house Electric Corp. (powder metallurgy type). The processing histories of these materials are listed in Table I. The first lot of are-cast molybdenum was deoxidized by aluminum additions. The second lot was deoxidized by carbon." Both lots of the powder Microstructure A microscopic examination of these materials, as received, revealed the powder metallurgy molybdenum to be free of inclusions and to be finely fibered. On the other hand, the are-cast C molybdenum possessed numerous carbide inclusions, and the arc-cast A appeared to have coarse grained fibers. These are shown in Fig. 1. Owing to the large apparent difference in fineness of fiber between the are-cast A and the powder product and are-cast C, a check was made of the recrystallized grain sizes to determine whether these differences persisted. A series of recrystallization anneals revealed mixed grain sizes in both the are-cast A and the powder product. Variations in grain diameter of as much as 50 times were found after full recrystallization at 1200°C for 30 min. There was no distinction between the two. Arc-cast C was not checked. Room Temperature Mechanical Properties Prior to subjecting the materials to fatigue tests, room temperature mechanical properties were determined. These data, together with the tensil: strength of the notched bars, data,togetherare listed in Table tensil: There were no significant differences in the tensile strengths of the two types of molybdenum. However, the powder metallurgy material was generally more ductile and yielded at a somewhat lower stress than the arc-cast material. Tensile strengths of the notched specimens indicated a slightly greater notch strengthening effect in the are-cast C than in the powder product, lot 2. Room Temperature Fatigue Properties Sample Preparation: Specimens were prepared for use in R. R. Moore rotating beam fatigue machines. These specimens had a continuous radius test section with a minimum diameter of 0.260 in. The specimens were prepared by grinding to shape and polishing to produce a smooth unworked surface. Polishing consisted of rotating a disk in the continuous radius section on which were attached, successively, emery belts of 240, 400, and 600 grit. The specimens were slowly rotated during the operation. The belt speed was high, and rotation was such that polishing scratches were longitudinal. Unnotched Fatigue Properties: Unnotched fatigue data were obtained from a number of specimens of each of the four lots of molybdenum. The results of the tests are presented in Fig. 2. From this figure,

Jan 1, 1956

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962

By A. D. McMaster, M. L. Gimpl, N. Fuschillo

There is interest in the use of rhenium metal films as resistive elements in thin-film circcits, and already some zvork has been done using er)aporated rhenium films. It has been found that rheniim films protected from the atmosphere by an evaporated layer of silicon monoxide show excellent electrical stability. Unprotected films, however, are subject to aging- effects, notably the increase in electrical resistivity as a function of time. This phenomenon can be understood as primarily one of oxidation of the thin films. This paper is concerned with the study of the oxidation and crystallization behavior of such unprotected films. It has been found that the oxidation rates are a function of the substrate temperatures used during the deposition of Lhe metal films. The strictures observed in the films are correlated with the film resistivities and some data are presented to establish the existence of the various types of oxides of rhenium. ThERE is some interest in the use of thin films of rhenium metal as resistive elements in monolithic, thin-film integrated circuits. Some work has been done using evaporated films and it has been found that such films, if protected from the atmosphere by an evaporated layer of silicon monoxide, show excellent electrical stability up to temperatures of 500"." Rhenium films unprotected from the atmosphere tend to age and the electrical resistivity of the films increases as a function of time. Rhenium films, of the order of <100A thick, prepared by electron-beam evaporation techniques are found to oxidize very readily when exposed to dry air at room temperature. It would seem, therefore, that this aging phenomenon could be attributed to the oxidation of the metal films. In this investigation, the oxidation and crystallization behavior of thin films of rhenium evaporated onto silicon monoxide substrates were studied as a function of the substrate temperatures used during the evaporation. The films were examined using electron-microscopy and electron-diffraction techniques. EXPERIMENTAL RESULTS Rhenium metal was evaporated onto suitable prepared substrates which were heated to various temperatures. The evaporations were performed in a vacuum of approximately 5 x 1CT5 torr. The evaporation was carried out at a rate of approximately 10A per omin. The final film thickness was approximately lOOA and the resistance ranged from 5000 to 10,000 ohms per square. The substrates used for supporting the metal films were made by evaporating 75A of silicon monoxide onto freshly cleaved mica. The silicon monoxide film was then floated off the mica by immersing the composite in water. The film could then be picked up on a clean nickel grid. Silicon monoxide substrates were chosen because of their similarity to quartz and glass substrates commonly used for making thin-film resistors. Fuschillo, Gimpl, and McMas-ter have also shown that silicon monoxide films have only minor structural changes at temperatures up to 800°C. This fact simplified the interpretation of any changes observed in the electron micrographs or electron-diffraction patterns obtained from the deposited rhenium films. After the evaporations were completed, the substrates were cooled to room temperature, except where noted differently, before the coated substrates were removed from the vacuum system. All aging of the deposited films was done in a desiccator. The evaporated films were examined in an electron microscope equipped with a hot stage that would permit continuous observations of the samples up to temperatures of 1000°C. RESULTS A series of electron micrographs of the rhenium films deposited on the silicon monoxide substrates are shown to Figs. 1 to 3. In all cases, the metal films are approximately 100A thick and the micrographs were taken 1 hr after the deposition was completed. here was no apparent structure in the films deposited on the substrates held at the higher temperatures. The

Jan 1, 1967

By J. E. Fox Jr., J. L. Lummus, J. P. Gallus

Fresh water or brine drilling fluids may be kept free of suspended drilled solids by the addition of a water soluble acrylamide-carboxylic acid copolymer at the flowline. Addition of from .01 to 0.2 lblbbl of the polymer solution to drilling fluids containing less than 5 per cent clay solids by weight causes the solids to flocculate and settle rapidly to the bottom of the pits. Solutions of the polymer injected at the pump suction reduce the loss of water to permeable formations without impairing the permeability to oil. The use of drill-itlg fluids clarified with the polymer has resulted in increased drilling rates, extended bit life, and lower drilling fluid costs. INTRODUCTION Field experience and the results of a number of investigations have established that the accumulation of solids in drilling fluid reduces drilling rate.&apos;-&apos; Drilling with water makes possible higher drilling rates than can be achieved with mud but in many areas drilling with water may not be feasible because of the possibility of encountering high formation pressures or by-dratable formations. To combat these conditions, the drilling fluid must possess certain physical properties such as viscosity, density, fluid loss, etc., which require the presence of solids. The current trend in drilling fluid treatment is to maintain as low a percentage of solids as is possible without harmfully affecting the mud properties needed for drilling. Mechanical separating devices such as wet cyclones and decanting-type centrifuges are proving to be an economical means of controlling the percentage of solids and thereby maintaining low solids muds. Also: special muds have been developed for the purpose of retarding the hydration of drilled solids so that they may be more easily removed by shale shakers or settling pits. In some areas, such as West Texas, the characteristics of some formations will permit drilling with water. However, because of the dispersion of drilled solids, it is usually not possible to maintain clear water even with the aid of mechanical separators, or by utilizing large settling pits. For this reason the commonly used term "water drilling" is a misnomer since the water usually contains some solids. Because of the improved drilling rates and other benefits which might be effected, a laboratory and field study was made of the use of flocculating agents for maintaining clear water for drilling. PROCEDURE Laboratory—Solids Settling Two techniques were employed to determine the effectiveness of flocculating agents in settling solids from drilling mud. First, the rate of fall of solids was measured in graduated beakers containing mud treated with various flocculating agents. Natural gum, oil-in-water emulsions prepared with ethoxylated nonyl phenols and diesel oil. and a powdered synthetic acrylamide-carboxylic acid copolymer* (hereinafter referred to as "polymer") were tested as flocculating agents in both fresh water and salt saturated muds containing 4 per cent solids. The polymer was not added in the powder form directly to the muds but was first dissolved in water in a concentration of 3.5 lb/bbl. The polymer solution was then added directly to the mud. The concentration of the flocculating agents, including the polymer, was varied. High rates of fall of the solids indicated high flocculating efficiency. A second technique consisted of measuring the time in minutes required to obtain clear water at the pump suction after addition of the various flocculating agents at the flowline. These tests were made using a model mud circulating system having a total volume of approximately 10 gal. The natural fresh water and brine muds used contained 4 per cent solids. A sketch of the circulating system appears in Fig. 1. The circulating rate