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By T. H. Alden

Using alternating tension-compression straining, the hardening of magnesium oxide single crystals was studied up to large stresses and strains. At 0.25 pct plastic strain amplitude, the hardening curve is approximately linear with slope 25,000 psi from the shear yield stress, 7 to 8000 psi, to 35,000psi. Above this stress, the slope decreases. The strain hardening behavior of MgO is considered qualitatively similar to that of metal single crystals. The relatively high stress attainable by strain hardening is associated apparently with the high yield stress on the cross-slip system, (001) <110>. Cleavage fracture during testing is uncommon. It is argued that the centers of high internal stress at glide band intersections, at which cracks tend to nucleate, are dispersed by cyclic strain. Special features of the glide band structure produced by cyclic strain and revealed by dislocation etch pits, support this view. Strain hardened MgO has mechanical properties greatly superior to the as-received material: yield stress, greater than 100,000 psi; elongation to fracture about 1 pct. A material is said to strain harden if the yield stress increases with an increment of plastic strain. This definition is usually applied for straining done in one direction, but is also applicable when the strain direction is periodically reversed, Fig. 1. For certain metal single crystals, data are available which permit a comparison of the hardening behavior for cyclic straining and for tension straining.&apos;-4 With certain qualifications, these data show that the same processes of hardening are operative in each type of test.5 Despite this fact, the importance of the technique is not immediately evident, although tension-compression studies of the common metals appear to suggest some deficiencies in theories of strain hardening developed exclusively on the basis of tensile tests. However, a recent observation suggests that the cyclic straining method may be very useful for studying semibrittle crystals in which large plastic strains are not accessible in unidirectional testing. The observation is that zinc crystals, when strained in tension-compression at -52°C, do not fail by cleavage at low stress (-500 psi)6 as they do in tension, but harden to a limiting stress of more than 5000 psi over a total plastic strain of about 600 pct.2 An important characteristic of the behavior of zinc crystals is the high stress, relative to the yield stress, attainable by strain hardening. By comparison, the hardening of aluminum single crystals tested by an identical technique saturates at 1100 psi. This difference is best explained by the cross-slip hypothesis of dynamic recovery.7,8 In zinc, cross slip is difficult because of the high yield stress for glide on planes other than the basal plane in the < 1120 > zone. The present work was undertaken in order to test whether these methods and ideas are applicable to other materials. Magnesium oxide single crystals, in common with most crystals of the rock-salt structure, deform plastically but fail by cleavage after a small strain when tested in tension. It was hoped that larger strains would be attained using tension-compression. There is, in addition, evidence 8a which shows that slip on the probable cross system, (001) < 110>, is difficult in magnesium oxide; it may therefore be possible to attain high stresses by strain hardening. 1) EXPERIMENTAL PROCEDURE Experimental methods used in this study were based in part on techniques reported in papers of Stokes, Johnston, and Li.&apos; MgO blocks, purchased from Norton Co., were used without further annealing. Specimens were cleaved to dimensions approximately 0.125 in. sq and 1 in. in length. The gage section, formed by chemical polishing, was sprinkled with 280 mesh silicon carbide particles in order to introduce fresh dislocations. The crystals were then cemented into cylindrical aluminum adapters and clamped in an Instron testing machine. One of two alternating straining programs was used. In the first, total cross-head travel was established and increased in steps after various numbers of cycles. In the second, a capacitance gage was used to directly measure the elongation of the specimen and the crosshead was controlled so as to keep the plastic strain amplitude constant. The straining was always symmetrical with respect to the initial, zero strain condition. While both procedures produce strain hardening, only the latter permits a measure of the total plastic strain so that hardening curves may be drawn. Constant plastic strain amplitude tests were done

Jan 1, 1963

By R. K. Dann, L. W. Roberts, R. B. Benson

The mechanical properties of 300-series stainless steels were investigated in both high-pressure hydrogen and helium environments at ambient temperatures. An auslenitic steel which is unstable with respect to formation of strain-induced a (bee) and € (hcp) mar-tensile is embrittled when plastically strained in a hydrogen environment. A stable austenitic steel is not embriltled when tested under the same conditions. The presence of hydrogen causes embrittlement at the mar-lensitic structure and a definite change in the general fracture mode from a ductile to a quasicleavage type. The embrittled martensitic facets are surrounded by a more ductile type fracture which suggests that the presence of hydrogen initiates microcracks at the martensitic structure. If a steel is unstable with respecl to fortnation of strain induced martensile, plastic deformation in a hydrogen environment will produce rapid embrittlement of a notched specimen in comparison to an unnotched one. FERRITIC and martensitic steels can be embrittled by hydrogen that has been introduced into the alloys, either by thermal or cathodic charging prior to testing.1-5 However, conflicting reports exist as to whether austenitic steels that are stable or unstable with respect to formation of strain-induced martensite can be embrittled by hydrogen.8-12 A recent investigation has shown that cathodically-charged thin foils of a stable austenitic steel can be embrittled.13 An earlier investigation of a thermally charged 18-10 stainless steel revealed a significant decrease in the ductility only at the lowest test temperature of -78°C, although strain-induced bee martensite was shown to be present in one specimen tested at ambient temperatures.&apos; When martensitic steels are tested in a hydrogen atmosphere, they are embrittled.&apos;4-&apos;7 It has been observed in this Laboratory that 304L steel, which is unstable with respect to formation of strain induced martensite, forms surface cracks when plastically strained in a high-pressure hydrogen environment. Work in progress elsewhere concurrent with this investigation has also established that 304L is embrittled when tested in a high-pressure hydrogen atmosphere." The objective of this investigation was to study the effect of a high-pressure hydrogen environment on the tensile properties of a stainless steel that contained strain-induced martensite (304L) and one that did not (310). EXPERIMENTAL TECHNIQUES Notched and unnotched cylindrical specimens were machined from 304L* and 310 rods that were heat- treated at 1000°C in argon for 1 hr followed by a water quench. The chemical analyses of these steels are given in Table I. The unnotched specimens had a reduced section diameter of 0.184 & 0.001 in., a gage length of 0.7 in., and were threaded with a 0.5-in.-diam. thread on each end. The notched specimens had a reduced section diameter of 0.260 * 0.001 in. and a 0.75-in. gage length, with a 30 pct 60 deg v-notch at the center. The notch had a maximum root radius of 0.002 in. The tensile bars were fractured in a hydrogen or helium atmosphere of 104 psi at ambient temperatures. The system used for mechanically testing the specimens is to be described in detail elsewhere.19 Several specimens of each type were tested in air using an Instron testing machine. The same yield strength and ultimate tensile strength were obtained in 104 psi helium with the above system as with the conventional testing machine. Magnetic analysis was employed to determine that there was a (bee) martensite in plastically deformed 304L and that it was not present in plastically deformed 310. The magnetic technique depended on allowing the material being studied to serve as the core between a primary and secondary coil. Thus, any change in the amount of magnetic material present between the annealed and plastically deformed steels will be indicated by corresponding changes in the induced voltage in the secondary circuit." The ratio of the output signal of a nonmagnetic stainless steel to a completely magnetic maraging steel was 2000 to I. Several unnotched 304L bars tested in hydrogen were analyzed for hydrogen by vacuum fusion analysis. There was an increase in the hydrogen content to approximately 2 ppm for the specimens tested in hydrogen, as compared to less than 1 ppm for the as-received material. Several thin sections cut from notched areas of 304L specimens tested in hydrogen and containing the fracture surface contained approximately 1.5 ppm H. The accuracy of these determinations was estimated to be ± 50 pct.

Jan 1, 1969

By Hollis L. Caswell

The present status of integrated circuits utilizing. superconductive switching. elements is reviewed with special attention given to fabrication techniques, methods for interconnecting completed circuits, and refrigeration requirements. Cryoelectronics has been largely an "inte- grated-circuit" technology since its conception because the switching speed of superconductive devices is attractive only when these devices are fabricated with thin-film techniques. It is true that cryotron circuits can be constructed from wires of appropriate materials (as indeed was done by Dudley Buck 1 in his early investigations) but these circuits will switch in times characteristic of milliseconds whereas similar circuits fabricated by thin-film methods have potential switching times of nanoseconds. Furthermore, cryo-electronic devices such as the cryotron lend themselves readily to fabrication by thin-film techniques since these components may be made from polycrys-talline thin films and are relatively insensitive to the presence of impurities (as measured by semiconductor standards). Therefore, during the past decade considerable effort has been devoted to developing techniques for batch fabricating circuit arrays containing superconductive switching elements. Technology had developed to the point several years ago that fabrication of cryoelectronic arrays containing up to one hundred devices was rather straightforward. However, larger arrays containing between lo4 and 106 components which are required for commercial development of cryoelectronics still pose very severe yield problems. Thus in a sense cryoelectronics found itself in 1962 at the point semiconductor technology finds itself today; namely, individual devices and small groups of integrated devices could be fabricated with acceptable yield and the outlook for building larger integrated-circuit arrays was bright. Unfortunately, problems associated largely with yield have made fabrication of these larger arrays difficult. Unlike semiconductor technology, cryoelectronics had to solve the problems of large-scale integration before it could become economically attractive. This has proven to be a sizable burden to bear. Since several reviews exist on superconductivity,2 superconductive devices,3 and cryoelectronic technology, no attempt will be made in this paper to summarize these areas. Instead a few specific topics will be dealt with in more detail. First, a brief description is given of selected superconducting switching and storage devices with special attention to several metallurgical techniques which improve the performance of these devices. Second, techniques used to fabricate cryoelectronic devices are described with emphasis on problems affecting yield. Third, techniques for interconnecting a number of cryoelectronic planes are described. And last, refrigeration of cryoelectronic components is discussed briefly since the low operating temperature of superconductive devices is an important consideration in this technology. SUPERCONDUCTING STORAGE AND SWITCHING DEVICES The basic superconductive switching device is the thin-film cryotron. The geometry of this device is attractively simple, since it involves only the intersection of two lines that are electrically insulated from each other. The switching element (gate) and control element (control) of a crossed-film cryotron are arranged as illustrated in Fig. 1. The material for the gate is selected to permit the gate to be switched from the superconducting to the normal (resistive) state by the application of a control current. Tin, which has a critical temperature (T,) of 3.7°K, is commonly used for the gate and the cryotron is operated at a temperature just below T, (for example, 3.5°K). The control material (normally lead, with T, = 7.2°K) is chosen so that the control is never driven normal during circuit operation. To improve cryotron operation, a ground plane, also of lead, is placed under all of the circuitry to act as a diamagnetic shield and improve the current-density uniformity across the width of various thin-film elements. Normally, line widths vary from 0.005 to ^ 0.020 in. and film thicknesses from 300 to 10,000A, although new fabrication techniques make narrower lines feasible. In fabricating cryotrons it is important that the edges of the gate elements be geometrically sharp to avoid undesirable switching characteristics associated with a thinner edge region, Fig. 2. One technique which has been used extensively to form patterns consists of placing a physical mask containing the film pattern between the evaporation source and the substrate and depositing through the mask. Film strips formed in this manner possess a penumbra at the film edges due to shadowing of the evapor-ant under the mask. Several techniques have been proposed for minimizing effects due to this penumbra. One of the more promising metallurgical techniques

Jan 1, 1967

By J. H. Brophy, S. J. Michalik

A constitution diagram for the system Mo-Ir has been determined. The maximum solubility of iridium in molybdenum is 16 at. pct at 2110ºC and decreases to less than 5 at. pct at 1500°C. The solubility of molybdenum in iridium is 22 at. pct. Three intermediate phases appear in the system: 8 MoJr, having the p-tungsten structure; a phase, a cornplex tetragonal structure; and the hcp ? phase. Metallography, melting point determinations, X-ray diffraction and fluorescence, and electron micro-probe unalyses were employed in establishing the diagram. PREVIOUS to the present investigation, the intermediate phases in the Mo-Ir system were identified, but no detailed account of the phase diagram has been reported in the literature. Raub1 investigated alloys of Mo-Ir over an extensive range of composition between the temperatures of 800º and 1600°C. The in-termetallic compound MosIr was found to exist with nearly pure molybdenum, as the solubility of iridium in molybdenum was not detectable parametrically in this temperature range. MO3Ir was found to be iso-morphic with a ß-tungsten type structure, having a parameter of 4.959Å. An intermediate hcp phase, designated as the ? phase, ranged in composition from 52 to 78.5 at. pct at 800ºC, and from 41 to 78.5 at. pct Ir at 1200°C. Parameters noted for the ? phase were as follows: at 42.7 at. pct Ir, a = 2.771i0, c = 4.4366, c/a = 1.601; at 78.5 at. pct Ir, a = 2.736A, c = 4.378A, c/a = 1.600. Molybdenum was found to be soluble in iridium up to 16.5 at. pct Mo (83.5 at. pct Irj, with the parameter of iridium increasing to 3.845A at the solubility limit. Knapton,2 who investigated alloys between 15 and 85 at. pct Ir, essentially agreed with Raub&apos;s data, but, in addition, found a a phase in as-melted alloys near 25 at. pcto Ir. The oaphase lattice parameters were a = 9.64Å, c = 4.96Å, c/a = 0.515. The a phase was replaced by the 8 -tungsten phase on annealing at 1600°C. Knapton concluded that the a was stable only at elevated temperatures, and placed the composition of the a phase at approximately 30 at. pct Ir. The intermetallic compound Mo3Ir, with a lattice parameter of 4.965A, was included among the 8-tungsten structures reported by ~eller.&apos; Matthias and Corenzwit,4 and Bucke15 studied the superconducting nature of MosIr, and reported a superconducting transition temperature of 8.$K. The present investigation describes the phase relationships in the Mo-Ir alloy system determined by melting point measurements, X-ray diffraction and fluorescence, and metallography. EXPERIMENTAL PROCEDURES Alloys for the determination of the phase diagram were prepared from powders. Commercial 99.9 pct Mo from Fansteel Metallurgical Corp. and 99.9 pct Ir powder from J. Bishop and Co. Platinum Works were used. The powders were weighed to nominal compositions, mixed, and then pressed, without binder, into compacts weighing 4 to 6 g. These were presintered in uacuo between 1200&apos; and 1400°C for 1 hr, to reduce the degree of spattering during subsequent arc-melting. The compacts were arc-melted in a nonconsumable tungsten electrode furnace six times on alternate sides on a water-cooled copper hearth in an atmosphere of zirconium-getter ed argon at 500 mm of mercury pressure. In almost all cases, this procedure yielded buttons of satisfactory homogeneity. The composition of all melted buttons were confirmed by X-ray fluorescent analysis using the experimentally determined ratio of the iridium La1 line intensity to that of the molybdenum Ka1 line as a function of composition. In this determination four alloys analyzed by wet chemical methods were used as standards. An uncertainty range of ±1 at. pct has been attributed to all indicated compositions. All heat treatments and solidus measurements were carried out in tantalum resistance heating elements in vacuum conditions of 10-4 to 10-5 mm of mercury. A detailed account of this procedure has been reported by Schwarzkopf and Brophy.8 In the heat treatment and solidus measurements of iridium-rich alloys (50 at. pct Ir or greater), a tungsten lining was inserted into the tantalum resistance heating element because of a eutectic reaction which occurs between iridium and tantalum at 1948ºc.7 Heat treatments and solidus measurements carried out at compositions less than 40 at. pct Ir both with and without tungsten linings within the resistance

Jan 1, 1963

By P. S. Kotval, O. H. Nestor

Stacking fault energy measurements of nickel-base alloys have been mainly confined to binary and ternary systems. In this paper, the stacking fault energy has been measured by the rolling texture method in a series of ten alloys which comprise successive additions of Cr, Mo, Fe, and C to pure nickel, eventually resulting in an alloy of the composition of Hastelloy alloy X. The alloys studied here are single-phase, solid solutions with the exception of two alloys in which some undissolved particles of "primary" carbide have been retained. It is found that successive additions of chromium, molybdenum, and iron all lower the stacking fault energy, with iron having only a minor effect. The stacking fault energy is found to increase when carbon is added in solid solution. The results from the rolling texture measurements are correlated with thin foil observations of dislocation substructures in these alloys. In a recent paper&apos; it was pointed out that the dislocation substructure of various superalloy matrices could be classified into three broad categories based on &apos;high&apos;, &apos;medium&apos;, and &apos;low&apos; stacking fault energy. It has also been demonstrated2 that the dislocation substructure in each of these categories has a well defined role in the nucleation of strengthening precipitates which is different from the role played by the dislocation substructure in other categories. Thus, it becomes desirable to understand the influence of various solute elements on the stacking fault energy and hence on the dislocation substructure of the matrix, before any further development of superalloys by mi-crostructural predesign can be undertaken. Recently, Beeston and France have studied the influence of increasing solute additions on the stacking fault energy of a series of binary nickel-base alloys relevant to the Nimonic series using the rolling texture method, and have then estimated the effect of a given alloy addition in five commercial Nimonic alloys. However, comparison with stacking fault energy data from other investigations&apos;&apos;5 suggests that the influence of a given solute element in a nickel-base binary system is not necessarily the same in a ternary or more complex superalloy system. Accordingly, the present work was undertaken to study the effect of successive addition of solute elements to pure nickel, the final composition being the nominal composition of Hastelloy X. The rolling texture method of stacking fault energy measurement was used since it can be used for the whole range of stacking fault energy values and does not have the disadvantage of, say, the Node method which is only applicable to low values of stacking fault energy. In addition, the rolling texture method provides a means of determining the stacking fault energy which is statistically more significant than that provided by other methods. EXPERIMENTAL TECHNIQUES Button heats of alloys of the compositions shown in Table I were prepared. Each button was remelted not less than four times. After a slight deformation (approximately 5 pct) all alloys were homogenized at 2200°F except alloys, H . I, and J. Alloys H and I were solution heat treated at 2150°F and alloy J at 2282OF. The buttons were cold worked by rolling, using "end-to-end" passes and intermediate anneals at the homogenization temperatures mentioned above. After each annealing treatment the samples were rapidly water quenched to avoid any precipitation. In alloys F and I, however, a few particles of "primary" carbides were retained even after the homogenization treatments at the temperatures mentioned above. Part of the solution heat treated material was cold worked to 0.04-in.-thick sheet and the penultimate reduction was -50 pct of deformation as recommended by Dillamore et al. All annealing was carried out in vacuo within sealed quartz capsules. Some of the material from each alloy was rolled down further to 0.004 in. strip for thin foil transmission electron microscopy specimens. Specimens of this strip were annealed at the homogenization temperature for 1 hr and then strained 7 pct by rolling at room temperature. Thin foils were prepared from the strip specimens by the &apos;window" technique using an Ethanol-Perchloric acid electrolyte at 32°F and a voltage of 22 v. Stainless steel cathodes were employed. All transmission electron microscopy was performed in a JEM-7 electron microscope using an accelerating voltage of 100 kv. Specimens from the 0.04 in. sheet which had been rolled -60 pct in the final pass were electropolished to remove the surface layers to a depth of approximately 0.002 in. Rolling texture pole figures for all the alloys were determined using a Schulz ring and nickel filtered CuKa radiation at 50 kv and 20 ma. The texture parameter Io/(lo + I,,) (where Io is the

Jan 1, 1970

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world&apos;s largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world&apos;s foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920&apos;s, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

By J. B. Campbell, V. V. Valleroy, B. T. Willman, L. W. Powers

A steam drive of heavy oil was field tested in a shallow, low oil-saturation formation near Deerfield, Mo. The pilot was conducted in the Warner formation, a sandstone containing an 18&apos; API oil having 1,000-cp viscosity at the 60F origind reservoir temperature. The formation war at a depth of 160 ft. Steam was injected into nine input wells arranged in an array of inverted five-spot patterns. In the completely confined center pattern, 14 temperature observation wells were installed to obtain thermal data and observe test progress. Late in the test, slugs of ammonia were injected to trace the flow paths of injected fluids. From the test area about 7,000 bbl of oil were produced. Data were obtained on areal and vertical temperature distribution, steam front advance, reservoir fluid movement and terminal saturations. This field test of a steam drive (I) demonstrated the feasibility of the method, (2) confirmed that the low residual oil saturations observed in the laboratory are obtained in the steam-swept region in the field and (3) provided recovery and conformance data for one set of field conditions. INTRODUCTION The Deerfield steam drive pilot test was conducted in a shallow sandstone containing 1,000-cp oil. The venture was undertaken cooperatively by the research and production departments of Carter Oil Co., which organizations have since been consolidated into Esso Production Research Co. and Humble Oil & Refining Co.. respectively. The production department was interested in steam injection at Deerfield because it appeared to be the most promising method of commercially producing this heavy oil deposit. The research department was interested in applying the new recovery method and in evaluating its performance in the field. At the time the test was begun, the initial oil saturation was not well known. Subsequent air coring and early pilot results confirmed that there was too little oil in place for profitable commercial exploitation by steam. Pilot termination at that time, however, would have been premature for evaluating field performance of the process, and the tert was continued to obtain additional data on steam injection as a recovery method. The test was located in Vernon County, Mo., about 10 miles north of the town of Deerfield and only a few miles from the Kansas border. The pilot site was selected as typical of the area. The location represented neither the highest nor the lowest oil saturation region in the acreage under lease in 1954. The steam drive was conducted in the Warner sandstone of Lower Pennsylvanian age. At the test site the top of the Warner occurs at about 160 ft subsurface and the formation is a fine- to medium-grained micaceous sandstone that dips gently to the northwest at the rate of 12 to 15 ft/ mile. A cross-section and permeability profile of the test location are shown in Fig. 1. At the pilot location the average total thickness of the Warner formation is about 43 ft, but the effective thickness for steam drive is 26 ft. Two distinct types of hydrocarbon saturation are apparent. The lower portion of the total sand, averaging about 17 ft thick, contains a very heavy asphaltic material that will not flow under the influence of a steam drive. This bottom interval, referred to as a dead oil residue, was not considered as part of the net sand undergoing steam exploitation. The initial formation and fluid properties of the upper 26 ft in the test area are summarized in Table 1, and variation of oil viscosity with temperature is shown in Fig. 2. Imbibition tests on preserved core samples taken at the end of the pilot test showed that the Warner sandstone was then neutral or slightly water-wet. Initially, the reservoir may have been strongly water-wet as indicated by low relative permeability to water during both water injection testing and early steam injection. PRIOR HISTORY Initial production tests of wells at the pilot site produced water with only a faint show of oil. No gas was produced except at Well 7-W in the pilot area and at another well about 1/3 mile northeast of the pilot. Prior to the start of the steam drive, a two-well water injection test and a two-well air injection test were conducted. No oil was produced by either. Water was pumped into Well I-W in the northeast corner of the pilot area with simultaneous production from Well 1 (Fig. 3). The air-injection tat was run at input Well 9-W and its offset, Well 2, in the southwest corner. Air and water injectivities were about the same when corrected for viscosity and pressure differences.

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,&apos; published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By G. A. Swanquist, E. M. Morales

INTRODUCTION The idea of water management and control at the Church Rock Mill operations began to take shape in February 1979. At that time, we were already investigating the feasibility of decreasing the fresh water requirements so that the solids would become the limiting factor in tailings impoundment utilization. The area for solution evaporation could be kept at a fraction of the normal requirements under the standard process of full water usage. The Church Rock Mill is an acid leach circuit followed by solids/liquid separation with thickeners in counter current decantation, and solvent extraction. Following the normal design of acid leach circuits, reuse of tailings solution was not incorporated in the original mill process design. INITIAL WATER CONTROL INVESTIGATIONS The investigations to decrease the fresh water requirements centered around modifying the grinding circuit from the present semi-autogenous grinding (SAG) mill in closed circuit with hydrocyclones, to open circuit grinding with a rod mill. The open circuit grinding with the SAG mill and rod mill in series had the potential of decreasing the water requirements for grinding and leach dilution by approximately 50% or 1.4 m3/min (300 gpm). The grinding pulp density would be maintained at 70 to 72% solids, and the leach dilution to 50% solids would be accomplished with acid tailings liquor recycle. In such a grinding circuit arrangement, the SAG mill would provide the primary or coarse grind, and the rod mill would be used for the fine grind. By the SAG mill and rod mill series grinding method of water control and other secondary water controls in various places downstream from the grinding circuit, the required necessary evaporation area was estimated at 120 acres of liquid surface. A second method of water control at grinding was investigated. A two-stage cyclone classification circuit appeared to have a good potential of achieving the same water reduction at a much lower capital and operating cost. However, in retrospect, this would not have been a viable method since a high slime recycle load would have been established hindering classification. The use of reagents to neutralize the acid tailings solution was not considered seriously at that time, since it would have materially increased operating costs, although it would have also allowed more tailings solution recycle and consequently, less fresh water usage. However, with the tailings solution deposition area available at that time, it was not then necessary to incur the high cost of neutralization. The control expected by the series grinding of semiautogenous and rod mills would have been sufficient to maintain a water consumption/evaporation equilibrium well in line with the available land area. IMPLEMENTATION OF NEUTRALIZATION OPERATIONS During the summer of 1979, the UNC Church Rock Mill experienced a tailings dam breach which resulted in a prolonged mill shutdown. Upon resumption of operations at the end of October 1979, tailings deposition was restricted to a small portion of the tailings impoundment area. Figure 1 shows the general tailings area and the limits of the present deposition area in the central part including the borrow pits. These borrow pits had been excavated to provide materials for tailings dam construction. Immediately after resumption of operations, it became evident that it would be necessary to control the quantity of liquid to be evaporated because of the small confined area available for tailings solution deposition and to maximize the deposition time in the tailings area. The water control required had to be exercised on a large scale, and to be in operation as quickly as possible. An obvious solution was to reuse the tailings liquor in mill process. Immediate steps were taken to install the necessary equipment for tailings neutralization on an interim basis. Anhydrous ammonia was selected as the primary neutralization reagent since it was the quickest system that could be placed in operation. Previous laboratory tests indicated fair results with ammonia neutralization. Such a system required a minimum of installed equipment and handling. INITIAL NEUTRALIZATION OPERATIONS Actual neutralization operations began on November 26, 1979. The raffinate solution which normally would have been discarded was pumped to a 3.7 m (12ft) diam by 4.3 m (14ft) tank for reagent contact, see Figure 2. At this tank, anhydrous ammonia was added directly from the tanker trailers and controlled at pH 7.0 nominally. Agitation was provided by air sparging. The neutralized product formed a highly viscous slurry in the grinding circuit which resulted in pumping and cyclone classification problems.

Jan 1, 1982

By J. S. Rinehart, W. C. Maurer

The mechanics of impact crater formation in rock, particularly sandstone, has been sutdied, the velocity range being approximately that normally associated with oilwell gun perforators. The bullets were small steel spheres having diameters of 3/16, 9/32 and 7/16 in; impact velocities ranged from 300 to 7,000 ft/sec. The craters have two distinct parts — a cylindrical hole (or burrow) with a diameter the same as that of the impacting sphere, and a wide-angle cup comprising most of the volume of the crater. The burrow is fornred as material in front of the projectile is crushed and pushed aside, forming a cylindrical hole surrounded by a high-density zone. The clip forms as fractures are initiated in front of the projectile and propagate along logarithmic spirals, approximaling maximum shear trajectories, to the free surface of the rock. A most significant observation (made for the first time) was that, below the base of the cup in one type of sandstone, there are a group of similar fractures, not extending to the surface, which are spaced uniformly a few millimeters apart. Each fracture follows roughly the contour of the base of the cup and appears to require a certain threshold impulse to initiate it. These fractures comprise a relatively high fraction of the total, newly exposed surface area. The volume of the material removed by crushing varies as the first power of the impact velocity and the volume removed by fracturing, as the second power of the impact velocity. Penetration varies linearly with the impact velocity and is inversely proportional to the specific acoustic resistance of the target material, the proportionality constant being dependent upon the shape of the projectile. INTRODUCTION Yield of oil from a producing well is frequently enhanced by firing bullets and shaped charges through the well casing into the oil-bearing rock, forming craters and fractures from which oil can flow more readily. The purpose of this investigation has been to develop a better understanding of the mechanics of impact crater formation in rock, particularly sandstone, the velocity range being approximately that normally associated with oilwell gun perforators. FORCES OPERATIVE DURING IMPACT When a projectile moving at considerable velocity strikes a- massive target such as oil-bearing sandstone, intense and complex transient stress situations develop within both the projectile and the rock or sandstone against which it is striking. Usually the struck rock fails, the missile or projectile penetrating into the rock to some depth where it comes to rest or is forcibly ejected from its burrow by expansion of a plug of target material compressed in front of it. When the impact velocity is very high, the projectile itself may fail, breaking apart or becoming distorted; this situation is not considered here, the discussion being limited to nondeforming projectiles. Many experimental studies&apos;.&apos; have been carried out to determine the nature of the mechanics of crater formation and the salient features of the forces coming into play, some of the earliest studies being the French Army experiments performed at Metz between 1835 and 1845.&apos; The stratagem in most instances has been to make a post-mortem examination of the crater, measuring volume and depth of penetration and deducing force relationships from these observations rather than performing the more difficult (usually almost impossible) feat of measuring stresses during penetration. In many materials, the force acting during penetration of the projectile is found to be the sum of two components—(1) a constant force, independent of the velocity, representing some inherent strength of the target material; and (2) a component, proportional to the square of the velocity, representing inertial forces. For such materials, the average force per unit area acting on the projectile at any instant while it is in motion and being decelerated may be written F/A = a + bv2 . . . (1) where v is the velocity of the projectile at that instant, A is the cross-sectional area of the penetrating projectile taken normal to its trajectory, and a and b are constants which are dependent upon the target material and the shape of the projectile. It follows that the total penetration s is given by .........(2) where v, is the velocity of the projectile when it just strikes the target. Values of a and b for spherical projectiles impacting in a loose sand-gravel mixture and compacted earth were obtained in the Metz experiments. For sand-gravel, a and b are 620 psi and 0.0115 (psi) (ft/sec)&apos;, respectively; and for compacted earthworks, a and b are 432 psi and 0.0008 (psi) (ft/sec)&apos;. Figs 1 and 2

By George B. Clark

Many basic engineering principles of all four phases of mining operations, namely, prospecting, exploration, development, and exploitation, can be analyzed better in terms of quantitative geology. Geological data from both field and laboratory will also complement scientific methods now being developed. THE geological data emphasized so successfully in prospecting for new deposits, that is, structural controls, strength of solutions, and type of mineralization, are basically those required for successful exploitation. In the mining of newly discovered deposits the most economical methods should be employed as early as possible to keep the overall cost per unit produced at a minimum and to permit maximum extraction of valuable minerals. A crucial question is: How can geological data be translated into useful quantitative results which will aid in achieving this end? H. E. McKinistry&apos; has suggested that a solution may be reached in one of two ways: 1—the usual approach, use of judgment based on experience; or 2—mathematical calculations and tests on models, both subject to certain limitations. He also suggests that in addition to better use of geology more case data and theoretical data are needed on which to base sound judgment. Further research, therefore, is necessary. Perhaps in this field the emphasis should be on more specialization in mining methods and ground movement by men with thorough training in physics, engineering, geology, and underground mining. These specialists would be equipped to point out the most economical and scientific methods of exploitation. Selection of a stoping method is governed by the amount and type of support a deposit will require in the process of being mined, or by the possibility of employing the structure of the deposit to advantage in mining the ore by a caving method. In addition to these factors there are others which almost invariably influence the choice of an economical method of mining:&apos; 1—strength of ore and wall rocks; 2—shape, horizontal area, volume, and regularity of the boundaries of the orebody, and thickness, dip and/or pitch of the deposit and individual ore shoots; 3—grade, distribution of minerals, and continuity of the ore within the boundaries of the deposit; 4—depth below surface and nature of the capping or overburden: and 5—position of the de- posit relative to surface improvements, drainage, and other mine openings. In the final analysis it is usually necessary to disregard the less important of these factors to satisfy the requirements of the more important. Because of the variation of geological conditions throughout and surrounding the deposit, no mining method will be everywhere ideally applicable to the conditions encountered in one ore deposit. The immediate problem is to interpret the above physical characteristics of deposits in terms of geological characteristics. Very few quantitative geological data are available on the factors related to a choice of mining methods. However, there are many descriptive data in mining and geological literature which collectively show how important an effect details of geology have upon all phases of mining operations. The following categories of basic mining methods were investigated to establish the geological factors that have affected their successful application: 1— open stopes with pillars; 2—sublevel stoping; 3— shrinkage stoping; 4—cut-and-fill stoping; 5— square-set mining; 6—top slicing and sublevel caving; and 7—block caving. It should be noted that the first five of these methods are listed in the order of increasing support requirements. Mines were selected as examples only where geological descriptions were complete enough to warrant their use. A study of the geological factors involved in mining operations led to a choice of the following classifications, employed in Table I: 1—structural type of orebody; 2—dimensions (geometry); 3— country rock (type); 4—faulting, folding, and fracturing; 5—alteration of ore and rock; 6—type of mineralization; and 7—geological factors determining mining method (summary). Of these factors only one yielded results that can be defined from available data in a quantitative manner, i.e., dimensions of the deposit. These are the most reliable guides that can be used in selection of suitable mining methods. They are, in general, the properties of geologic structure most difficult to evaluate by studies of models, pho-toelastic studies, and other laboratory methods, all of which are at present more limited in their applications than the geologic method. Application of geology has proved a reliable guide in other phases

Jan 1, 1955

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal&apos; and by Chew and Connally&apos; for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7&apos; API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.&apos; All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By Robert W. Hendricks, John B. Newkirk

A simple method is described for determining the orientation of a single crystal by means of a cylindr cal X-ray camera. Orientation setting to within ±1 deg is attainable by a stereographic analysis of a single cylindrical Laue pattern produced by the originally randomly mounted crystal. Final precision adjustments which permit orientation of the crystal to within ±5 min of arc from the desired position can be made by the method of Weisz and Cole. A chart, originally Presented by Schiebold and schneider7 and which allows a direct reading of the two stereographic polar coordinates of the corresponding pole of a given Laue spot, has been recomputed to aid in the stereographic interpretation of the cylindrical Laue X-ray photograph. Detailed instructions for the use of the chart, a simple example, and a comparison with the conventional flat-film Laue Methods, are presented. 1 HE problem of determining the orientation of the unit cell of a single crystal relative to a set of fixed external reference coordinates is fundamental to most problems of X-ray crystallography and to many experimental studies of the structure-sensitive physical properties of crystalline materials. Several techniques for measuring these orientation relations have been developed which correlate optically observable, orientation-dependent physical properties to the unit cell. Examples of such procedures include the observation of cleavage faces or birefringence, as discussed by bunn,1 or the examination of preferentially formed etch-pits, as discussed by barrett.2 Each of these methods is limited, for various reasons, to an orientation accuracy of approximately ±1 deg—a serious limitation in some experimental studies. Several other limitations decrease the generality of these methods. Of these, perhaps most notable is the absence in many crystals of the physical property necessary for the orientation technique. The most widely used methods for determining crystal orientation are variations of the Laue X-ray diffraction method. Because of the indeterminacy of the X-ray wavelength diffracted to a given spot, the interpretation of Laue photographs is now limited almost exclusively to the procedure of using a chart to determine the angular coordinates of the corresponding pole for each spot. For the flat-film geometries, either a leonhardt3 or a Dunn-Martin4 chart is used in interpreting transmission patterns, whereas a greninger5 chart is used for interpreting back-reflection patterns. A less common method of interpreting flat-film transmission Laue photographs is by comparing the Laue pattern with the Majima and Togino standards,6 or with the revised standards prepared by Dunn and Martin.4 Although this last method is applicable only to crystals with cubic symmetry, it can be very rapid and just as accurate as the graphical methods. The primary limitation of all the X-ray methods mentioned is the relatively small number of Laue spots and zones which are recorded on the flat film. Often, few, if any, major poles appear, thus making interpretation tedious and sometimes uncertain. The use of a cylindrical film eliminates this problem. Schiebold and schneider7 prepared a chart by which the orientation of the specimen crystal could be determined from a cylindrical Laue photograph. However, it was only drawn in 5-deg intervals of each of the two angular variables used to identify the Laue spots, thus limiting the accuracy of orientation to about ±3 deg. An examination of this chart indicated that if it were drawn in 2-deg intervals, crystal orientations to ±1 deg would be attainable. Subsequent use of the replotted chart has confirmed this accuracy. It is the purpose of this paper to describe the redevelopment and use of this chart, and to point out its advantages and limitations. I) CAMERA GEOMETRY AND CHART CALCULATIONS The geometry of the cylindrical camera with a related reference sphere is shown in Fig. 1. The X-ray beam BB&apos; pierces the film at the back-reflection hole B, strikes the crystal at 0, and the transmitted beam leaves the camera at the transmission hole T. One of the diffracted X-rays intersects the film at a Laue spot L. The normal OP to the diffracting plane bisects the angle BOL between the incident and diffracted X-ray beams. The point P on the reference sphere can be located uniquely by the two orthogonal motions 6 and 8 on the two great circles ENWS and BPQT respectively. Because the Bragg angle 8 (= 90 - < BOP) is always less than 90 deg, P always remains in the hemisphere BENWS. Therefore, if every possible pole P is to be recorded on the same stereographic projection, it is necessary that the projection reference point be at T with the projection plane tangent to the sphere at B.* The great

Jan 1, 1963

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400&apos; to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,&apos; in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886&apos;C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.&apos; This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2&apos;6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7&apos;9 These effects were observed at testing temperatures in the range 100 to 300&apos;. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.&apos; These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180&apos; was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio &apos;c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4&apos;5 dense patches or clusters of prismatic dislocation loops, planar arrays,4&apos;10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10&apos; life level the

Jan 1, 1969

By Eckhard Nembach

The phase diagram of the system Pb-In has been investigated between -27° and + 40°C, using nzainly X-ray dijfraction. In accordance with t her mo dynamic measurements by Heumann and Predel, a segregation occurs at low temperatures, though not in the form of a nziscibility gap. THE phase diagram of the system Pb-In has been the subject of extensive investigations,1&apos;1 but recently Heumann and prede13 concluded from their thermodynamic data that a new feature should occur below room temperature. These authors observed that the maximum values for the enthalpy and entropy of mixing, which occurred at a composition of 50 at. pct Pb, were +400 and —1.7 cal per g-atom deg, respectively. From this the authors estimated that a miscibility gap should occur below 30°C, centered at 50 at. pct Pb. Resistivity measurements seemed to support this view. These authors proposed the phase diagram outlined in Fig. 1. Three phases exist at 30°C: the tetragonal indium phase with c/a > 1, the tetragonal intermediate phase a, with c/a < 1, and the fcc lead phase. During an investigation of the superconducting properties of Pb-In alloys. it has been observed4 that aging a specimen with 50 at. pct Pb for 14 days at -18°C decreased the superconducting transition temperature about 0.13"K and tripled the transition width. In this paper, the results of an investigation of the Pb-In phase diagram in the temperature range from — 2T to +40°C are reported. Superconductivity and X-ray methods have been used. 1) SPECIMEN PREPARATION The materials were provided by the American Smelting and Refining Co. According to the manufacturer their purity was 99.999 pct. The weighed amounts of the constituents were sealed in quartz tubes under an atmosphere of 10 torr helium, mixed for 24 hr in a rocking furnace at 380°C, quenched in ice water, and homogenized at 20" to 30°C below the solidus line, established by Heumann and Predel. The annealing times were 144 hr for specimens containing Less than 30 at. pct Pb and 36 hr for the remainder. 2) SUPERCONDUCTIVITY EXPERIMENTS The specimens were quenched from the homogeniza-tion treatment into ice water and their superconducting transition temperatures T, measured. The procedure used has been described in Ref. 4. The transition was detected by the change of the mutual induc- tance of two coaxial coils containing the sample. T, was defined as the temperature at which 50 pct of the total change in inductance had occurred. The repro-ducibility with which T, could be measured was i0.002"K. Then the specimens with lead contents between 38 and 75 at. pct were aged for 7 days at temperatures between -30" and 40°C. If this treatment caused T, to change by more than 0.005"K or the width of the transition to increase by more than 0.002"K, it was concluded that the specimen had undergone a phase change and no longer consisted only of the fcc lead phase: as it did immediately after homogenizing. The result is shown in Fig. 2. From this one can estimate at what temperatures and concentrations phase changes occur. The X-ray measurements were based on these preliminary results. 3) X-RAY EXPERIMENTS Because of the softness of the material, relatively coarse powders. 75 p, had to be used, which were filed in a helium atmosphere from homogenized specimens. The powders were annealed at least 30 min at temperatures between 120" and 16OJC, depending on their concentration, and quenched in ice water. Then their X-ray patterns were taken at -178°C with a Picker diffractometer, model 3488K, and a cold stage. on which the specimen was in thermal contact with a liquid-nitrogen reservoir. In this way the following relation was established for the fcc lead phase: a = 4.697 + 0.00247C for 40 5 C 5 75 11 where n is the lattice constant (A) and C is the at. pct of lead. The coarseness of the powder made it impossible to use lines with 0 > 75 deg; therefore n was averaged from lines with 45 deg 5 0 5 75 deg. The results were reproducible to within i0.05 pct. Relation [I] is very similar to the one found by Heumann and Predel at room temperature. Following this, homogenized specimens with compositions between 15 and 56 at. pct Pb were aged for at least 10 days at temperatures between -27" and

Jan 1, 1970

By M. Bevis, A. F. Acton, P. C. Rowlands

Defor~nation twinning and transformation twinning modes most likely to be operative in Fe-Ni and Fe-Ni-C martensites have been determined using a new theory of the crystallography of deformation t~inning.~ This analysis shows that potentially important conventional and nonconventional twinning modes1 have been omitted in previous analyses. Discussion is given on the relevance of the predicted twinning modes to the lattice invariant shear associated with the martensite transformation in steels and to anomalous deformation twinning in Fe-Ni-C martensites. THE two most important criteria which appear to govern operative twinning modes in metallic structures1 are that the magnitude of the twinning shear should be small and that the twinning shear should restore the lattice or a multiple lattice in a twin orientation. The latter criterion ensures that the shuffle mechanism required to restore the structure in a twin orientation is simple. These criteria have been adhered to in the prediction of twinning modes2"6 in bcc and bct single-lattice structures with axial ratios in the range y = 1 to 1.09 as, for example, encountered in martensite occurring in steels. Refs. 2 and 3 in particular consider the martensite transformation in steels and the twinning modes in these cases relate to transformation twinning, and hence the lattice invariant shear associated with the martensite transformation. The list of twinning modes which can be compiled from these sources is incomplete and the ranges of magnitude of shear considered could be unrealistically small, particularly in the case of deformation twinning. The latter consideration is supported by the fact that twinning modes with magnitudes of shear large compared with the smallest shear consistent with a simple shuffle mechanism have been established in, for example, the single-lattice structure mercury7 and the multiple-lattice structure zirconium.&apos; In addition the anomalous deformation twins reported by Ftichrnan4 to occur in a range of Fe-Ni-C martensites still remain unexplained. It is clear that a comprehensive analysis of twinning modes likely to be operative in martensite In steels is required. The results of the application of a new theory of the crystallography of deformation twinningg to these structures are presented in this paper. The theory has been used to determine all shears which restore the lattice or a multiple lattice in a new orientation with magnitude of shear up to a required maximum. The orientation relationships between parent and twinned lattices are not restricted to the classical orientation relationships of reflection in the twin plane or a rotation of 180 deg about the shear direction. PREDICTED TWINNING MODES Twinning modes which restore all or one half of lattice points to their correct twin positions will be referred to as m = 1 and m = 2 modes, respectively. These modes are the most likely to describe operative modes in single lattice structures. The bcc m = 1 and m = 2 modes which have magnitudes of shear s in the range s < 2 and s < 1, respectively, have been given10 and are reproduced here in Tables I and 11. Detailed discussion of the crystallography of these modes and cubic modes in general will be discussed elsewhere (~evis and rocker, to be published). The four twinning elements Kl, &,ql,7)2 as well as the magnitude of shear s are given for each twinning mode, and the twinning modes are given in order of increasing shear. Two twinning modes are given in each row of the tables, the twinning mode Kl, Kz, ql, q2 and the reciprocal twinning mode with elements Kl = K,, Ki = Kl, q: = q2, and 17; = ql. The m = 1 and m = 2 twinning modes which describe twinning shears with small magnitudes of shear and simple shuffle mechanisms in bct crystals with -y = 1 to 1.09 are given in Tables I11 and IV, respectively. On increasing the symmetry of the tetragonal lattice to cubic, that is making y = 1, all modes listed in Tables 111 and IV must reduce to crystallographically equivalent variants of the modes given in Tables I and 11, respectively, or become twinning modes with both shear planes as symmetry planes in the cubic lattice and hence not considered in Tables I and 11. With the exception of this last type of mode only those tetragonal twinning modes which reduce to modes 1.1, 1.2, 2.1, and 2.2 of Tables I and I1 are considered in Tables 111 and IV. For values of y in the range -y = 1 to 1.09 the tetragonal modes and the corresponding cubic twinning modes have approximately the same magnitude of shear. The twinning modes listed in Tables 111 and IV are therefore by the criteria given above the most

Jan 1, 1969

By R. W. Balluffi, R. Resnick

NUMEROUS investigations of chemical diffusion in a brass have been made and the results are collected in several places.1-3 This work has been mainly concerned with the determination of the chemical diffusivity as a function of composition and temperature. In 1947 Smigelskas and Kirken-dall&apos; showed that zinc and copper diffuse at different rates in face-centered-cubic brass, and since then, a number of efforts have been made to determine the intrinsic diffusivities of zinc and copper in this alloy.1, 5-9 Horne and Mehl8 in particular have recently determined the intrinsic diffusivities as functions of temperature and composition using sandwich-type couples and inert markers. Inman et al." also have determined the intrinsic diffusivities in homogeneous alloys using tracer techniques. When the present work was started, no information of this type was available. Consequently, measurements of the intrinsic diffusivities were made as a function of temperature at a constant composition of 28 atomic pct Zn with vapor-solid diffusion couples where the zinc was diffused into the diffusion couple from the vapor phase. The application of these couples to the study of diffusion in a: brass has been described previously.0,7 The temperature dependence of the intrinsic diffusivities was found to follow the relation D, = A, exp(-Hi/RT) and the values of Hzn, and Hcu, were found to be closely the same. It is emphasized, however, that the chemical dif-fusivity (D = N1D2 + N2D1) is a composite diffusivity and does not necessarily follow this exponential form. It is usually found to do so within experimental error for substitutional alloys because the heats of activation of the intrinsic diffusivities generally are not greatly different.&apos;" Also, at the onset of this work, there was no information available concerning possible unequal diffusion rates of individual components and the existence of a Kirkendall effect in alloys with other than face-centered-cubic structures. Since then, two reports indicating a Kirkendall effect in body-centered-cubic ß brass have appeared. Landergren and Mehl" have published a note describing Kirkendall diffusion experiments with sandwich-type couples. Inman et a1.9 also find a Kirkendall effect in this alloy using the tracer technique. In the present work, several aspects of the Kirkendall effect in ß brass were further investigated using vapor-solid couples. Two different couples were used, one in which the zinc was diffused into the specimen from the vapor phase and the other in which the zinc was diffused out of the specimen into the vapor phase. Briefly, the existence of a Kirkendall effect is confirmed and it is found that Dzn/Dcu = 3 at about the 46 atomic pct composition in this alloy at 600°, 700°, and 800°C. As a result of the unequal diffusion rates of zinc and copper, volume changes occur and subgrain formation is observed in the diffusion zone. In addition, significant porosity is produced by the precipitation of supersaturated vacancies. Diffusion in this alloy is therefore outwardly similar to diffusion in a brass where these effects are also observed, a Brass Experimental Methods—The use of vapor-solid couples in studying diffusion in a brass has been described in previous articles.6,7 The method briefly consists of sealing a copper specimen with Kirkendall markers initially placed on its surface in an evacuated quartz capsule along with a large zinc source of fine a brass chips and then diffusing the zinc into the specimen through the vapor phase. The zinc concentration at the specimen surface rises rapidly enough to a value near that of the a brass source so that the surface concentration may be regarded as constant during diffusion. Under these boundary conditions, values of the chemical diffu-sivity may be obtained by applying the Boltzmann-Matano analysis to the concentration penetration curve, and the intrinsic diffusivities may be obtained from Darken&apos;s5 equations when the velocity of marker movement is known. The diffusion specimens were made from OFHC copper in the form of disks 3.2 cm diam and 0.5 cm thick with faces surface-ground parallel to within +0.001 cm. Markers in the form of fine alumina particles <0.0002 cm diam were placed on the specimen surface. These specimens were then sealed in quartz capsules along with enough a brass chips of a 30.0 atomic pct Zn composition to keep the source concentration from decreasing by more than 0.3 atomic pct Zn as a result of the loss of zinc to the specimen during diffusion. The quartz capsules which were initially evacuated to a pressure of

Jan 1, 1956

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.&apos; The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.&apos; and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,&apos; or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969