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By R. K. Hopkins

Fox a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By A. J. Jacobs, J. W. Spretnak, R. Speiser

The activities of nickel in liquid iron-nickel solutions containing from 10 to 90 at. pct Ni were measured over the temperature range .1510° to 1600°C. A special function was devised whereby activities can be computed by a graphical integration using the results of chemical analyses on the vapor phase alone. The liquid solutions studied exhibit negative deviation from Raoult's law, but they approach ideality as the temperature is raised from 1510° to 1600°C. The maximum heat of solution is less than -8.0 kcal per mole. The entropy of solution is less than —2.5 kcal per mole deg at 1510°C, and changes negligibly as the temperature is raised. The liquid iron-nickel solutions do not follow regular solution behavior. THE activities of the components of a liquid alloy system can be determined in favorable cases from the partial pressure of the vapor in equilibrium with the liquid alloy.' Assuming that the vapor over the alloy behaves as an ideal gas, the activity of component i is given by the expression, Where the superscripts 1, v, and o signify the liquid, the vapor, and the pure component, respectively; the f's are the fugacities, and the P's, the pressures. The quantities Pi and Pi can be determined by the

Jan 1, 1960

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of 'composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert's-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.' The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967

By Arthur W. Gray

The thermal analysis of a metal or an alloy is ordinarily made with the aid of heating and cooling curves in which transitions are indicated by the rapid changes in curvature that accompany changes in the rate of heat absorption or evolution. Analysis by the method that depends on the change in thermal expansivity is not customary, partly, at least, because of the difficulties involved in making the necessary measurements. However, under certain circumstances, the dilatometric method of analysis may possess advantages over the thermometric method that will justify the additional trouble required. The addition of 1 per cent. of zinc to an alloy has been found to produce upon the volume changes that take place during transition effects that suggest the possibility of using the dilatometric method of thermal analysis as a rather sensitive means of obtaining chemical information. Although the illustrations presented in this paper are drawn from data obtained during an investigation of dental amalgams, similar phenomena can doubtless be observed with other alloys. Some of the results found during an investigation made in 1917l have been confirmed by data on the thermal expansivity of amalgams published by Souder and Peters of the Bureau of Standards in reporting tests of dental materials.2 Although the Bureau of Standards made experiments for the purpose of discovering effects of including zinc as one of the constituents of a dental alloy—a matter much discussed in dental literature but without the presentation of reliable experimental evidencae to support the views of either side—the reports of the tests made by the Bureau give the impression that certain striking phenomena associated with the presence of zinc were not noticed. Among such phenomena arc those connceted with the conditions that determine whether or riot a specimen of amalgam becomes covered with droplets from which crystals develop.

Jan 1, 1921

By C. E. Sims, C. A. Zapffe

AN investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. APPARATUS The apparatus is shown in Fig. I and the system is shown by diagram in Fig. 2. Furnace Atmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In [ ] this furnace free oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1942

By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick's First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood's analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner's diffusion-controlled kinetics is based upon the same form of mass balance using Fick's First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

By I. R. Kramer

Single crystals of aluminum were pulled in tension in a solution of paraffin oil and stearic acid. The critical resolved shear stress did not change with the concentration of the stearic acid solution; however, the extents and slopes of Stages I and II were affected greatly. The observations lend evidence that the weakening effect of surface-active agents is controlled by the rate of desorption of the metal soap formed by the reaction of the surface-active agent and the metal surface. IT has been shown by various investigators1-" that surface-active agents markedly affect the mechanical properties of single crystals. (A surface-active agent, for the purpose of this report, is defined as a long-chain organic molecule which contains one or more polar groups. Usually, however, investigations have considered only molecules having one polar group.) In general, when single crystals are deformed in some solutions containing surface-active agents, the creep rate, Fig. 1, is increased and the yield strength is decreased. The fatigue strength has been reported to be affected also.ll Rehbinder and his asociatesl' explained the "weakening" effect of surface-active agents in terms of physical adsorption. They assumed that a large pressure was created in microcracks which existed on the surface of the crystal." Harper and Cottrell,' from their study of the effects of surface conditions, found that the deformation characteristics of zinc single crystals were not altered by a solution containing a surface-active agent unless the surface of the specimen had an oxidized surface. They concluded that the role of the polar molecule was to remove the strengthening effect of the oxide coating. Later, And-radeetBpresented additional evidence which appeared to agree with this conclusion. In contrast, Klinken-berg et al.7 reported data which confirmed the results of Rehbinder. Using zinc and cadmium crystals which had been cleaned by electrolytic polishing, a large increase in the creep rate was observed when Lle specimens were tested in a 1 pct oleic acid-paraffin oil solution. They also reported that the creep rate

Jan 1, 1962

By A. T. Goldbeck

THE use of stone as a building material in relatively large blocks is recorded in ancient historical records but only within the past 200 years has broken stone in small sizes begun to have extensive use, principally in highway construction. Tresaguet, in 1764, describing his method for highway construction in France, required the top surface to be built of stone about the size of a walnut, broken by the use of a hammer. It is said that the Romans, in the top layer of their rather massive roads, used large stones bonded together with lime mortar and bedded in small stones mixed with mortar. Much of the early macadam as built by McAdam around 1815 in England was made with hand-sledged broken stone. In 1858, the use of crushed or broken stone received a great impetus from the invention in that year by Eli Whitney Blake of what is said to be the world's first stone crusher. As a consequence of that invention, stone could be crushed to small sizes with considerable ease and, as a natural result, the use of crushed stone in macadam roads and as railroad ballast increased at a great rate. Also, as portland cement came into use, machine-produced crushed stone furnished readily available aggregate. Rapidly, other uses developed, such as for fluxstone in the production of pig iron and for other metallurgical operations and chemical utilizations. These utilizations made for the rapid growth of the crushed-stone industry and this growth is still proceeding with the growth of population and the development of new uses, notably the employment of limestone for the improvement of soils for agricultural purposes. The industries of which the production of crushed stone is a part have a tonnage second only to that of mineral fuel in the mineral industries of this country.

Jan 1, 1949

By Ulf S. Landergren

Diffusion coefficients and marker movements have been determined in brass using welded couples. Three different concentration ranges were employed at 750°C, while a fourth concentration range was measured at 500°, 600°, 700°, and 800°C. Marker displacements toward and porosity development in the high zinc side of the couple were observed in all cases. The results were interpreted as favoring a vacancy diffusion mechanism. IN the large amount of diffusion literature which has accumulated during the past half century, very few experimental data have been presented on body-centered-cubic metallic phases. The impressive combination of experimental and theoretical studies which has given the vacancy mechanism a fairly secure position as the preferred mechanism for most face-centered-cubic metals has no counterpart for body-centered-cubic phases, although the theoretical picture seems to be in a better state than the experimental work. The attempts to select diffusion mechanisms by the theoretical calculation of the activation energy for the various conceivable unit diffusion processes and the energy of formation of the type of lattice defect required have been based on models of two kinds. The first kind utilizes potential functions fitted for certain properties of pure crystalline copper; the second kind is fitted for sodium. The latter is an example of an open metal in which the metallic ion is small compared with interatomic distance,&apos; while the former is characteristic of the larger class of metals in which the ions have diameters about as large as the interatomic distance. brass should resemble copper in this fundamental property. It should be evident that results on the mechanism of diffusion obtained for one of these classes need not necessarily apply to the other. Huntington and Seitz, using a model of the copper type, showed that the activation energies to be expected for interstitial migration or a two-atom direct interchange were much higher than that for vacancy diffusion. Zener pointed out that a four-atom ring rotation would involve an activation energy considerably lower than the two unlikely mechanisms although still higher than the vacancy mechanism in the face-centered-cubic structure. Furthermore, he argued, the four-atom rotation would be relatively easier in a body-centered-cubic lattice and might be competitive with the vacancy mechanism. Paneth showed that a body-centered-cubic crystal-like sodium could form interstitial defects of special type, called a crowdion, by crowding an extra atom into < 111 > directions where the defects would affect a line of about eight atoms. The defect was constrained to move along the defining line. Unlike the face-centered-cubic case, therefore, the theoretical calculations for the body-centered-cubic mechanism do not provide a very clear-cut answer, and the absence of adequate experimental studies is the more serious. This investigation was undertaken for the purpose of obtaining useful information on diffusion in body-centered-cubic phases. brass was chosen for several reasons: 1—the phase field is sufficiently wide at high temperatures to permit the use of diffusion couples with adequate concentration ranges for satisfactory chemical analysis, 2-—thermodynamic activity data are available for the calculation of mobilities from diffusion coefficients, 3—the phase is as close to the theoretical model of the copper -type on which the calculations have been done as any body-centered-cubic metallic phase is likely to be. Measurements of the movements (if found) of inert markers during the diffusion process would indicate that a vacancy or Or mechanism played a major role in diffusion in brass. If no marker movement should be found, a ring mechanism would be indicated but not assured. Experimental Procedure The alloys used in these experiments, listed in Table I with analyses, were supplied by the Naval Research Laboratory. They were from ingots of 3x3 in. cross-section, heated to 760°C, reduced under a

Jan 1, 1957

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The effects of increasing hydrogen content, introducing a notch, and changing the strain rate on properties of titanium and one of its alloys were investigated over a range of testing temperatures from —196° to 200°C. Both high purity and commercial purity A-55 titanium were used as representative a materials, while a commercial Ti-8 pct Mn alloy was used for an a-P alloy. It was found possible to analyze the data, using the ductile-to-brittle transition temperature concept. Increasing hydrogen, the presence of a notch, and increasing the testing speed raised the transition temperature for the a materials. The presence of hydrogen and notches raised the transition temperature of the a-B alloy also. However, increasing the testing speed generally decreased the transition temperature of the a-p alloy. IN previous papers, the authors have shown that hydrogen is most detrimental to the notch-bend impact toughness of a-titanium&apos; and to the tensile ductility of a-B titanium alloys.&apos; These general effects have been confirmed by Kessler and co-workers," and by Kotfila and Erbin." Kessler showed that the slower strain rate in notch-rupture tests was a more sensitive measure of hydrogen embrittle-ment of a-B alloys than the tensile test. In the present paper the authors cover, with tensile and notch-bend tests, the effect of testing speed, notches, and testing temperature on hydrogen em-brittlement. High purity and commercial purity titanium, examples of u materials, and a commercial a-,f3 Ti-8 pct Mn alloy were investigated. The purpose of the investigation was to correlate the factors producing embrittlement. Materials The high purity titanium for this investigation was obtained by arc-melting crystal bar from Foote Mineral Co. into 1 Ib ingots. As-cast hardnesses for these ingots ranged from 60 to 90 Brinell. The arc-melted ingots were forged to % in. diam rods at 1470°F. These rods were swaged to & in. diam at room temperature prior to machining of the specimens for hydrogenation and testing. The commercial A-55 titanium and the Ti-8 pct Mn alloy were obtained from Rem-Cru Titanium Inc., as % in. diam rod. The A-55 titanium was hot swaged to 1/4 in. diam at 1300°F prior to machining of the specimens for hydrogenation and testing. The a-p C-11OM alloy was hydrogenated prior to hot swaging to 1/4 in. roc1 at 1300°F. Hydrogenation prior to fabrication permitted testing of the a-P alloy in the equilibrated and stabilized condition. The equilibration and stabilization treatment used was an air anneal for 1 hr at 1300°F, followed by furnace cooling to 1100°F and then air cooling. Hydrogenation was done in a Sieverts apparatus described previously.&apos; The hydrogenation treatment consisted of heating for 1/4 to 1/2 hr at 820 °C in purified hydrogen, slow cooling to 680"C, holding 1 hr for homogenization, and rapid cooling to room temperature. Intended hydrogen levels for the a-tita-nium materials were 0.05, 0.5, 1.0, 1.5, and 2.0 atomic pct—about 15 to 430 ppm. For the Ti-8 pct Mn alloy, the intended hydrogen levels were 0.05, 0.5, 1.0, 2.5, and 5.0 atomic pct—about 15 to 1100 ppm. The material for the 0.5 atomic pct level of hydrogen was vacuum annealed prior to hydrogenation to increase the accuracy of the addition. Vacuum annealing to remove hydrogen consisted of heating for 6 hr at 820°C, and resulted in a hydrogen content of about 10 to 15 ppm. When hydrogen contents were above 0.5 atomic pct—100 ppm—the hydrogen was added without prior vacuum annealing.

Jan 1, 1957

By William E. Harris

Time and experience have demonstrated that by means of the Waelz process zinc, lead, cadmium, arsenic, antimony, bismuth and tin can be volatilized satisfactorily. In this way difficult gold ores are being treated to allow for the recovery of the precious metal. Iron ore containing zinc is being treated to remove the zinc and recover the iron. In Germany, thallium is being recovered in commercial quantities from the zinc oxide fume; indium, germanium and gallium are also concentrated to a degree warranting recovery, even though these rare metals are only recognizable in the ore by means of the spectroscope. The physical, chemical or mineralogical condition of the raw material affects very little the applicability of the process. The name Waelz is derived from the German word Waelzen, meaning a "trundling motion," which very aptly describes the movement of the charge through the slowly rotating kiln. The recovery of zinc and lead by volatilization in a rotary kiln has its origin in a process patented in 1910 by Edward Dedolph, of British Columbia. The Dedolph patent was taken over by the Metallgesell-schaft of Frankfurt-on-Main, Germany, which in cooperation with the Griesheim-Elektron, now a part of a large industrial combine, introduced certain improvements (Ohlmer, Specketer patents), but without bringing the process to a state suitable for large-scale operations. The war temporarily stopped all work on the process, and it was not until after the war that the Krupp Grusonwerk, of Magdeburg-Buckau, Germany, quite independently of the Metallgesellschaft, instituted research work in this field of metallurgy, which in 1923 led to the Waelz process proper. The Krupp Grusonwerk and the Metallgesellschaft A.G. later on collaborated, and by their joint efforts further developed and perfected the Waelz process, which they are marketing together as "Waelz-Gemeinschaft." The process is capable of treating a varied type of material; for instance, oxidized and sulphide zinc ores, calamine (zinc carbonate ore) waste dumps, jig tailings, jig slimes, table concentrate slimes, brass ashes, zinc-bearing iron ores (where the iron sinter is the real objective and the zinc oxide a by-product), electrolytic-zinc leach residues, zinc muffle residues and works sweepings, lead-furnace slags, tin ores and slags, anti-

Jan 1, 1937

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th&apos;vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1&apos;2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS&apos; and on GaAs doped with oxygen,5&apos;" manganese,&apos; and copper.&apos; The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By William Fink

NICKEL is used as an alloying element in several complex commercial aluminum alloys, among which are found some very interesting proper-ties, such as relatively high strength at elevated temperatures, relatively low coefficient of expansion, the absence of permanent growth, ability to take a good polish, and a bright, pleasing as-cast surface. For that reason the aluminum-nickel system was included in the list of binary aluminum systems that are being studied as a preparation for the investigation of more complex commercial alloys. This paper is the fifteenth of a series from the Research Laboratories of the Aluminum Company of America reporting the results of investiga-tions of equilibrium relations in aluminum-base alloys of high purity. The aluminum-nickel equilibrium diagram from 0 to 18 per cent nickel was determined, using the purest material available.

Jan 1, 1934

By Chester A. Rowland, David M. Kjos

Mineral ore comminution is generally a feed preparation step for subsequent processing stages. Grinding, the fine product phase of comminution, requires a large capital investment and frequently is the area of maximum usage of power and wear resistant materials. Grinding is most frequently done in rotating drums utilizing loose grinding media, lifted by the rotation of the drum, to break the ores in various combinations of impact, attrition and abrasion to produce the specified product. Grinding media can be the ore itself (autogenous grinding - primary and secondary), natural or manufactured non- metallic media (pebble milling) or manufactured metallic media - steel rods, steel or iron balls. This chapter covers rod and ball mills which utilize manufactured metallic grinding media. Fig. 1 shows the cross section of an overflow rod mill, Fig. 2 an overflow ball mill, and Fig. 3 a diaphragm (grate) discharge ball mill.

Jan 1, 1978

By Michel T. Halbouty

The area for which oil and gas developments in South Texas are reported for 1940 in this paper covers the same counties that were included in the reports for 1938 and 1939, with the addition of LaSalle County. LaSalle County is includcd in the Laredo district of South Texas, which totals seven counties for that district. The Corpus Christi district remains the same, with nine counties. The two districts together comprise what is known as the South Texas area for this report. Continued exploration along established trends and beyond proven field limits during 1940 provided South Texas with new fields and new producing levels at a rate of discovery fairly comparable with the high records set during recent years. The wells drilled in the counties within this district (including LaSalle) numbered 1656, approximately 8 per cent below the 1801 figure of last year. However, rank wildcats totaIed 336, an increase of 17.5 per cent compared to the 286 drilled in 1939. Therefore, since new field discoveries numbered 25 in 1940 against 29 in 1939, the rate of new field discoveries in 1940, based upon rank wildcats drilled, was I/I3.4 while that of 1939 was I/9.86, which shows a decrease of about 25 per cent in the rate of new fields. The rank wildcat tests in 1940 gave the following results: 18 produced oil, 4 produced distillate with gas, 3 produced. only gas, and 3r1 were dry holes (Table 5). Of the 1320 tests drilled in already proven fields or as extensions to pro+en areas (representing a decline of 12.8 per cent from last year&apos;s total of 1515 tests), 1048 produced oil or distillate, 60 produced gas and 212 were dry holes (Table 4). Of the producers, 50 found new sands or crude-in-distillate-sands in existing fields. Among the several fields subjected to extensive development were: Colorado, Jim Hogg County; East White Point, San Patricio and Nueces County; Rincon and Sun, Starr County; Glen, Webb and Zapata Counties; Wade City and Orange Grove, Jim Wells County; Stratton and South Clara Driscoll, Nueces County, and Aransas Pass, San Patricio and Aransas Counties. The development of important crude reserves on structures formerly considered primarily distillate fields has probably been the most important phase of the year&apos;s operations in South Texas. The Rincon, Stratton, Agua Dulce, Wade City, Odem and Robston fields provided the new crude sand discoveries. At some places crude production was opened by exploratory wells that found new sand horizons; in others by flank wells that found already discovered distillate sands sufficiently low to provide crude production. Rincon, Starr County, with its multiple sands, is now believed to be one of South Texas&apos; largest crude-oil reserves. Offshore drilling showed important results during the year, including the discovery of two new submerged fields and the extension of the East White Point field into offshore Nueces County. The new marine fields are: East Flour Bluff) 76

Jan 1, 1941

By Michel T. Halbouty

The area for which oil and gas developments in South Texas are reported for 1940 in this paper covers the same counties that were included in the reports for 1938 and 1939, with the addition of LaSalle County. LaSalle County is includcd in the Laredo district of South Texas, which totals seven counties for that district. The Corpus Christi district remains the same, with nine counties. The two districts together comprise what is known as the South Texas area for this report. Continued exploration along established trends and beyond proven field limits during 1940 provided South Texas with new fields and new producing levels at a rate of discovery fairly comparable with the high records set during recent years. The wells drilled in the counties within this district (including LaSalle) numbered 1656, approximately 8 per cent below the 1801 figure of last year. However, rank wildcats totaIed 336, an increase of 17.5 per cent compared to the 286 drilled in 1939. Therefore, since new field discoveries numbered 25 in 1940 against 29 in 1939, the rate of new field discoveries in 1940, based upon rank wildcats drilled, was I/I3.4 while that of 1939 was I/9.86, which shows a decrease of about 25 per cent in the rate of new fields. The rank wildcat tests in 1940 gave the following results: 18 produced oil, 4 produced distillate with gas, 3 produced. only gas, and 3r1 were dry holes (Table 5). Of the 1320 tests drilled in already proven fields or as extensions to pro+en areas (representing a decline of 12.8 per cent from last year&apos;s total of 1515 tests), 1048 produced oil or distillate, 60 produced gas and 212 were dry holes (Table 4). Of the producers, 50 found new sands or crude-in-distillate-sands in existing fields. Among the several fields subjected to extensive development were: Colorado, Jim Hogg County; East White Point, San Patricio and Nueces County; Rincon and Sun, Starr County; Glen, Webb and Zapata Counties; Wade City and Orange Grove, Jim Wells County; Stratton and South Clara Driscoll, Nueces County, and Aransas Pass, San Patricio and Aransas Counties. The development of important crude reserves on structures formerly considered primarily distillate fields has probably been the most important phase of the year&apos;s operations in South Texas. The Rincon, Stratton, Agua Dulce, Wade City, Odem and Robston fields provided the new crude sand discoveries. At some places crude production was opened by exploratory wells that found new sand horizons; in others by flank wells that found already discovered distillate sands sufficiently low to provide crude production. Rincon, Starr County, with its multiple sands, is now believed to be one of South Texas&apos; largest crude-oil reserves. Offshore drilling showed important results during the year, including the discovery of two new submerged fields and the extension of the East White Point field into offshore Nueces County. The new marine fields are: East Flour Bluff) 76

Jan 1, 1941

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano&apos; (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.&apos; It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12&apos;13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By A. W. Adamson

A model for transport processes in liquid mixtures is discussed which supposes that the elementary act involves a position exchange between two species and that the exchange is so confined by the solvent cage as to occur nearly isosterically. The rate-determining step, thus, is likened to a bi-molecular reaction and is so treated, using absolute rate theory. The cage model has been applied to diffusion, thermal diffusion, sedimentation and viscosity, but only the first and last of these phenomena are emphasized in the present paper. The model leads to semi-empirical relationships between the absolute value for a digusion coefficient and the activation energy for diffusion, between mutual and self-diffusion coefficients and for the variation of the viscosity of a binary mixture with composition. These are discussed in relation to experimental data for various systems, including hydrocarbon mixtures. It is shown that the proposed viscosity equation and seven other commonly used ones all may be regarded as special cases of a single general relationship; a brief critical analysis is made of the basis of selection of one or the other for data fitting or interpolation. INTRODUCTION AND GENERAL THEORY The present paper covers a brief discussion of a cage model for transport processes in liquid mixtures and how this model may be useful in treating the diffusional behavior and the viscosity of such systems. Since diffusion requires the more detailed treatment, it will be taken up first, and the model then applied to viscosity. There are two types of diffusion coefficients that may be measured experimentally, apart from thermal diffusion quantities. The first is the mutual or binary diffusion coefficient, D which may be defined in terms of Fick&apos;s first law. This states that the permeation, or flux P, is proportional to the concentration gradient. In the usual experiment, P is measured relative to a frame of reference fixed with respect to the medium (e.g., the diaphragm in a diffusion cell); as a consequence, the same value of D is obtained regardless of whether P and C refer to Component 1 or to Component 2; i.e., there is only one independent mutual diffusion coefficient for a binary system. In addition to D there will be various self-diffusion coefficients. defined in terms of the gradient in labelled species i and its permeation in an otherwise uniform medium. The thermodynamic approach to mutual diffusion supposes that the actual driving force is the gradient of the chemical potential, i.e., that In the case of a dilute solution of solute, Eqs. 1 and 3 lead to the Einstein equation, If the solution is ideal and the friction coefficient is taken to be then the familiar Stokes- Einstein equation results. Mutual and self-diffusion coefficients can not be related on general thermodynamic grounds; it is necessary to invoke some additional assumptions, i.e., a model; several such have been proposed. Hartley and Crank&apos; supposed the existence of separate, intrinsic diffusion coefficients (Dl and D2) for each component, essentially corresponding to the two self-diffusion coefficients. The two flows can not be independent, however, but must be coupled through the usual restriction that there be no net volume flow. For an ideal solution. one then obtains&apos; Glasstone, et al&apos; treated diffusion in terms of absolute rate theory, but their approach otherwise resembled the previously mentioned one in that each species was considered to move with respect to the general medium in a manner determined by its individual jump distance and specific rate constant. For other than dilute solutions, a coupling of flows leading to an equation such as Eq. 6 would again be present. However, as required by Eq. 6, one does expect that the self-diffusion coefficient for the solute and the mutual-diffusion coefficient for the system become identical at infinite dilution. Lamm4 recognized that there should be three distinctive interactions in a two-component system-1-1, 1-2 and 2-2 — and, therefore, proposed three rather than two fundamental friction coefficients. Mutual diffusion resulted from 1-2 interactions only, and self-diffusion resulted from 1-2 plus either 1-1 or 2-2 interactions. Again, a collective coupling between all motions was imposed to meet the condition of no net volume flow. Laity&apos; has shown how to convert the Onsager equations to a form very similar to Lamm&apos;s. Cage Model For Diffusion Work in this laboratory on diffusion in aqueous sucrose solutions made it apparent that three, rather than two, interactions were indeed needed," but considera-