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By A. F. Crowley, D. W. G. White

AS part of a continuing program of liquid metals research, the densities of liquid lead, tin, zinc, cadmium, and indium have been measured by a pycnometric method. The pycnometers are made of high-density graphite to the design illustrated in Fig. l(a). In pursuing this research program, emphasis has been placed on detailed experimental care. As a result, claims are made for densities accurate to within ± 0.05 pct over temperature ranges varying from about 100° to 200°C above the melting point. A paper reporting the densities of tin, lead, and Pn-Sn alloys has recently been published,' while papers dealing with

Jan 1, 1969

By Bernard Porter

Differential thermal analysis measurements were used to characterize a phase diagram for the KF-YF3 system at compositions between 0 and 60 mole-percent YF3, A congruent melting point compound was observed at 3KF?YFs, which melts at 965°±5° C and undergoes solid-state decomposition at 725°±2° C. One peritectic and two eutectic compositions are also defined.

Jan 1, 1969

By R. W. Stormont, F. Wald

The phase diagram of the Pseudobinary section PbTe-Fe was determined. It was found to contain a monotectic and a eutectic reaction, the latter one taking place at 14 at. pct Fe and 875° * 5°C. The solid solubility of iron in PbTe was found to be 0.3 at. pct by electronmicroProbe analysis. No solubility of PbTe was detected in iron. Slight deviations from true pseudobinary behavior were found to occur in the range of - 5 to 10 at. pct Fe. In the course of a general investigation of reactions of various metals with lead and tin telluride,' the lead telluride-iron system was reinvestigated. It had been established much earlier than iron does not chemically react with lead telluride but forms a eutectic with a melting point of 879" The eutectic composition or other related information has never been reported, but for a number of years iron has been in general use for contacting of lead telluride and lead telluride alloys for thermoelectric applications. It seems therefore desirable to clarify the exact constitution of the system to furnish a base for the long-term evaluation of bonds made between lead telluride and iron either by pressure contacting or by brazing methods. I) EXPERIMENTAL METHODS Lead telluride-iron alloys were prepared in 10-g charges, using premelted lead telluride. This material was prepared from high-purity, semiconductor-grade lead and tellurium obtained from the American Smelting and Refining Co. and described as 99.999 pct pure. The iron used was "Armco" iron; the major impurities found here were 0.02 pct C, 0.018 pct Si, and 0.015 pct Cr. All remaining impurities were less than 0.01, the total of all impurities not exceeding 0.15 pct. Charges were prepared in closed quartz arnpoules which were evacuated and in some cases backfilled with high-purity argon to retard excessive lead telluride evaporation and deposition in slightly cooler parts of the ampoule. For high iron concentrations, this can lead to total separation of the constituents, since the vapor pressure and the sublimation rate of PbTe are quite high.4 Nevertheless, since the ampoules are closed, no change in overall composition was expected and the nominal composition of all alloys was assumed to be retained. X-ray diffraction analysis, thermal analysis, and microsections were used in the evaluation of the alloys. The nature of the system was such that X-ray diffraction was not particularly helpful. It merely served to establish that at all concentrations PbTe and a! iron were in equilibrium at room temperature. Thermal analysis was carried out by taking direct temperature vs time curves on a Sargent recorder where a width of 10 in. was kept as 1 or 0.5 mv by use of an automatic bucking voltage network. Quartz ampoules with minimized dead space, coated with boron nitride and fitted with a thermocouple reentrant, were used as containers for the charge. At high temperatures and over long periods of time, boron nitride reacts with iron. For the thermal analysis runs, however, this was not significant. More significant was the fact that the vapor pressure of PbTe at some of the meas -uring temperatures apparently exceeded I atrn quite considerably. This, in some cases, caused the slightly softened quartz tubes to blow out if great care was not taken to contain them and minimize time and temperatures used. As containers pure nickel tubes were used which also served to avoid temperature gradients in the quartz ampoule. Nevertheless, the experimental difficulties at high temperatures were severe and the monotectic temperature could therefore not be determined accurately. In general, the accuracy reached by the thermal analysis setup in this case is *4"C as determined with gold, silver, and tin, under the conditions of analysis here. Inherently, the apparatus is capable of reaching accuracies better than i 1°C. Also, difficulties were encountered in microsection-ing. They were related to polishing, since it is rather difficult to avoid pulling the iron out of the weak and brittle lead telluride matrix. It proved best to follow a procedure where, after grinding to 600 grit on carborundum paper, a polish with 6 p diamond was used on nylon cloth. Finally, #3 "Buehler" alumina and an automatic polisher were used for -5 min only, to avoid relief. The best etching results were achieved with

Jan 1, 1969

Over the last decade mineral exploration in New South Wales has increased markedly. This is due to various factors including the influx of overseas companies an. capital, increase and stabilization of metal prices and improvements in exploration techniques. The initiation of full-scale petroleum exploration and recent discoveries of large mineral deposits in the west, north-west and north of Australia has increased overseas capital, and brought scientists and technicians into the country. Naturally there has been an overflow into New South Wales, which is less attractive as an area for new and large-scale discoveries. In some fields, rise in metal prices and price stabilization has largely contributed to the intensif- ication of exploration. Increased tin production in New South Wales since 1963 is a direct result of price rise and stabilization, and rise in the price of silver has revived an interest in silver prospecting in recent Years,

Jan 1, 1969

By C. W. Dwiggins

The Bureau of Mines characterized the chemical and physical properties of metallo-organic materials in petroleum to determine their effect on petroleum production and refining. The structures and physical properties of porphyrins and materials that normally contain metalloporphyrins such as crude oils and asphaltenes were investigated using elemental analysis, NMR analysis, absorption spectrometry, and small-angle X-ray scattering. Petroleum fractions greatly enriched in metalloporphyrins were obtained using asphaltene precipitation, liquid extraction, and large-scale liquid-solid chromatography. Selected fractions containing porphyrins were further purified by chromatographic methods, crystallization, and demetalation followed by chromatography. Nonporphyrin metals could not be appreciably concentrated from the bulk of the asphaltene.

Jan 1, 1969

By Colin J. Dixon

The full realization of the potential of computers in geological in- formation system demands new approaches to the machine representation of information. At the same time, the feasibility of such a system, particularly in commercial field, demands greater freedom in input preparation and a degree of standardization in the arrangement of subject matter system. The paper describes some of the basic notions of project "GEOSEMANTICA 70". The aim of the project is to devise means of storing real geological informations in a machine rather than the representation of the information in human language form. This is seen as the only long-term solution to the problems of the complex vocabulary of geology and the complex syntax of geological description. Effectively, a machine language is being defined, consisting of a set of symbols and a date structure for representation of geological and related information. Beyond this, is the definition of a set of rules allowing the use of constrained text as an input/output medium. The investigation is oriented primarily to the representation and handling of information about mineral deposits and the associated geographic, economic and engineering information.

Jan 1, 1969

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By C. L. Pillar

In the capitalistic system the success of a mining enterprise is measured by the rate of return on the investment and the speed by which its redemption is achieved. Exploration in search of ore deposits often results in the emergence of the lean orebody which does not meet basic company requisites. At this point a decision must be made whether to place the orebody into production or postpone production pending more favourable market conditions. The wisdom of this decision, borne out by future results, demonstrates the quality of a company's management and is instrumental in the degree of financial success it achieves. The project feasibility report must show a rate of return on the capital invested that is attractive to the company, plus its full redemption in the desired period of time, in order to bring the property into production on a sound economic basis. Mining companies have demonstrated their ability to bring the profitability of a marginal property from a point that says "no go" to a point of "go" by substantial reduction of expenditure without adversely affecting production rate or cost. Here is where the real challenge exists for today's mining engineers and plant designers; they will have to develop better ideas and concepts: ideas that will still allow maximum production at reduced capital expenditure, This is the sound way marginal orebodies can be brought into production without inflationary increases in the price of their product.

Jan 1, 1969

By Webster Smith

El cobre se encontró en Cornwall al mismo tiempo que el estaño debido a que ambos elementos se encuentran asociados en las minas. En ese sentido, el presente texto señala las primeras minas de cobre en Inglaterra, como las primeras prácticas de fundición de este metal, las fuentes medievales de cobre inglés, las fuentes de mineral más antiguo del extranjero, la expansión del cobre en la antigua China y en la antigua Grecia y Roma.

Jan 1, 1969

By M. I. Jacobson, A. S. Yue, A. E. Vidoz, F. W. Crossman

An equation governing the concept of constitutional supercooling under the combined effect of concentration and temperature gradients was used to produce platelike Al-CuAl2 eutectic composites for mechanical properties studies. Compression specimens were prepared from a single-colony Al-CuA12 eutectic composite ingot, 2 in. in diam and 12 in. long. The specirrzens were cut such that the platelets were oriented parallel, 45 deg, and perpendicular to the compression direction. Since the ingot was of eutectic composition, The aluminum-rich matrix could dissolve 5. 7 wt pct Cu in solid solution, and therefore could be strengthened by precipitation hardening. Specimens were tested at room temperature and elevated temperatures in the unidirectionally solidified, solution-treated, and solution-treated plus aged conditions. The results were compared with those for the conventionally cast and extruded specimens. For the controlled material, the highest strengths were obtained with platelets oriented parallel to the compression axis. In the unidirectionally solidified condition, 0.2 pct offset yield strength was 32,000 psi; however, this was increased to 59,000 psi by solution treatment, and further increased to 90,500 psi by solution treatment and aging. The attainment of high compressive strengths in the Al-CuAl2 eutectic composites was interpreted in terms of the buckling of elastic CuAl2 platelets in the plastically deformed a aluminum matrix. SINCE the discovery of high-strength whiskers,' scientists and engineers have made significant progress toward incorporating these whiskers into metallic matrices, forming composites for basic studies and structural application. The general procedure is to produce the whiskers first and then to bind them together with a ductile matrix. The production of whisker-reinforced composites requires tedious handling techniques,, particularly when it is desired to align the whiskers unidirectionally. Furthermore, the interfacial bond between the whisker and the matrix is frequently poor3 so that the resulting composite has strengths lower than expected. These disadvantages are generally true for any metallic composite produced by physically mixing the components. It is possible to eliminate these shortcomings by growing whiskers directly in the matrix material by eutectic solidification.4-8 In eutectic solidification, the matrix phase and a whisker phase are grown approximately simultaneously from a liquid of the same overall composition at the eutectic temperature. If the solidification process is controlled by varying the freezing rate, the temperature gradient, and the impurity content, platelike or filamentlike whiskers are produced parallel to the growth direction. The morphology of the grown-in reinforcement, i.e.. plates or rods, generally depends on the volume fraction9 of the dispersed phase present in the eutectic mixture. Since the unidirectional eutectic solidification is a one-step process, i.e., the liquid-solid transformation process, an excellent interfacial bond between the matrix and whisker is obtained. An additional advantage is that no special handling technique for whiskers is needed. In recent years, many investigators10-13 have studied the effects of growth variables on the micromorpholo-gies of binary eutectic alloys produced by controlled solidification. The study of their mechanical properties was initiated by Kraft and coworkers14-16 who found that the strength of cast A1-CuA12 eutectic alloy can be increased threefold by unidirectional solidification. In the A1-AL3Ni system, a strength of 50,000 lb per sq in, was reported for the unidirectionally solidified eutectic alloy, a value five times higher than for conventionally cast material. Thus, the unidirectionally solidified eutectics can be used as fiber-reinforced composite materials. In this paper, we shall first use an equation17 as a guide for the production of eutectic composites in general and the Al-33 wt pct Cu eutectic in particular. Experimental data supporting the theoretical prediction are given. Second, the compressive properties of the grown A1-33 wt pct Cu eutectic were thoroughly investigated in terms of platelet orientations, thermo-mechanical treatment, and temperature. The experimental data are interpreted in terms of a buckling model of fibers in elastic fiber-plastic matrix metallic composites. EXPERIMENTAL PROCEDURE Crystal Growth. The following experimental procedure was adopted for the production of controlled microstructures in the A1-33 wt pct Cu eutectic alloy. The controlled solidification was accomplished with a movable resistance-wound radiation furnace. Fig. 1 is a schematic drawing of the solidification apparatus. A water-cooled chiller was placed into a degassed high-purity graphite crucible containing the charge. Rubber stoppers wrapped with aluminum foil were used to seal both ends of the quartz tube through which a dried argon atmosphere was passed under a slight positive pressure. At both ends of the quartz tube, radiation shields were used to minimize heat loss. The quartz tube was held in place by two steel clamps and the furnace was drawn vertically by means of a steel cable against the steel truss which permits the furnace to move without touching the tube. The drive mechanism consisted of two pulleys, a counter weight.

Jan 1, 1969

Jan 1, 1969

By E. C. Tveter, R. B. Tippin

The separation of minerals by heavy liquids is a standard laboratory technique which goes back at least 50 years, but commercially economic application of this principal to ore concenfration has been prevented by problems of liquid recovery. Recent investigations which demonstrate the different types of liquid-solid systems on various ores using the two major heavy liquids - methylene bromide and tetra-bromoelhane — are discussed in this article. As a result of these studies, over-all liquid recovery, and especially desorption of heavy liquid from the mineral surface, was improved by the use of surfactants as well as both thermal and mechanical energy. The examples given in the article indicate that heavy liquids which should find major commercial use in ore concentration are now available. The sink-float process using a heavy liquid medium has long been recognized as a nearly perfect method of mineral separation based on the differences in density of the minerals. The use of heavy liquid separation (HLS) offers the potential of an ore dressing method that provides the maximum possible natural concentrate grade and high recovery. In addi- tion the process requires no water, causes no waste disposal problems, and is extremely simple — the crushed ore is merely introduced into a liquid whose density is between that of the minerals to be separated. The minerals lighter than the liquid float while those heavier than the liquid sink. As such, HLS has become a standard laboratory tool but major commercial application has been prevented by the requirement for complete recovery of the heavy liquid, imposed by economics and materials handling hazards. Investigations, both in the United States and abroad, have shown that improved liquid stability as well as improved chemical engineering techniques brighten the future for HLS in ore dressing. The available commercial heavy liquids suitable for mineral separation cost from $2.00 to $20.00 per gallon1 and on this basis alone their complete recovery is economically desirable. Possibly of even greater importance is the fact that any residual heavy liquid remaining on the products could create a serious toxicity hazard. Consequently, to make the process commercially attractive requires (1) essentially complete removal of the liquid from the ore products and (2) optimum recovery of the liquid for reuse. Until recently these two stipulations have remained as obstacles but laboratory and pilot plant research now in progress suggests that these may soon be overcome. Various heavy liquid recovery systems have been proposed to meet these requirements and might be classified into one or more of the following three general classes: Solvent Wash (Fig. 1): The dissolution of the heavy liquid from the ore with a less expensive solvent,

Jan 1, 1969

Jan 1, 1969

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By H. N. Hall

Reservoir and producing characteristics can govern the decision to use either a one-, two- or three-dimensional model for making predictions for gravity-drainage reservoirs. Examples of conditions requiring one-, two- and three-dimensional calculations are given. In 1961 the author presented a method for predicting one-dimensional gravity-drainage performance. This work has been exrendcd to obtain a three-dimensional model, which is described and for which a sample problem is presented. Introduction Many papers on gravity drainage or gas-cap drive'-3 have been presented for conditions where the reservoir is treated as a single areal segment so that, in effect, only one-dimen-sional flow is considered. Other authors'-Q ave given evidence showing that the one-dimensional concept would be unsatisfactory to predict reservoir performance for certain types of reservoirs. Experience has indicated that specific reservoir and producing conditions govern whether one-, two- or three-dimensional concepts must be used as a basis for reliable reservoir performance predictioils. Previously the author presented a paper outlining a method for predicting the performance of gravity-drainage reservoirs.' That paper treated the reservoir as a single areal segment so that it was applicable for only one-dimensional flow. The work has been extended to obtain a three-dimensional model that can be used to predict performance of gravity-drainage reservoirs. Although capable of being three-dimensional, it can be used equally well for one- and two-dimensional predictions. This paper discusses those reservoir and producing conditions governing the choice of model, and also describes a three-dimensional model suitable for predicting reservoir performance in the more complex situations. Discussion The Choice of Model To predict reservoir performance, it is necessary to represent the reservoir by a physical model. A mathematical model, based on the assumed physical model, then is used to predict the movement of oil and gas within the reservoir. The word "model" is used here to connote the combination of both a physical model and a mathematical model based on the physical model. Certain types of reservoir situations may be predicted suitably with a one-dimensional model, whereas two- and three-dimensional models may be required for other situations. This section illustrates reservoir conditions associated with the use of a specific type of model. Many types of reservoir structures are such that gravity drainage possibly could be an important factor in oil production. Production practices, as well as the nature of the structure. can influence the type of model that should be used. obviously, it is impossible to discuss all combinations of reservoir structure and production practices that might be encountered in gravity-drainage reservoirs. The following are typical examples of conditions where a choice must be made among a one-, two- or three-dimensional model to predict reservoir performance satisfactorily. Conditions Requiring a One-Dimensional Model Fig. la shows contours for an asymmetrical anticline in which gravity drainage might be expected to be important. Fig. Ib depicts a cross-section along Line A-A in Fig. la. Existence of a gas cap is a good clue that gravity drainage will be an important factor in producing oil from this type of reservoir. However, it is not essential since a gas cap will form as oil is produced from the reservoir. If the proper combination of reservoir permeability and withdrawal rates is present, the reservoir will behave like a

Jan 1, 1969

By R. A. Vandermeer, J. C. Ogle

The preferred crystallographic orientations (texture) developed in randomly oriented, poly crystalline niobium during rolling were studied by means of X-ray diflraction techniques. The evolution of texture at both the surface and center regions of the rolled strip was carefully examined as a function of increasing defamation throughout the range 43 to 99.5 pct reduction in thickness. Certain aspects of the center texture development in niobium are in agreement with the predictions of a theory by Dillamore and Roberts, but others cannot be explained by the theory in its present form. Above 87 pct reduction by rolling, a distinctly different texture appeared in the surface layers which was unlike the center texture. The present results are compared with previous results obtained from other bcc metals and alloys. RANDOMLY oriented, poly crystalline metal aggregates when plastically deformed to a sufficiently large extent develop preferred orientations or textures. In a recent review article, Dillamore and Roberts1 pointed out that the nature of the developed texture may be influenced by a large number of variables. These include both material variables such as crystal structure and composition and treatment variables such as stress system, amount of deformation, deformation temperature, strain rate, prior thermal-mechanical history, and so forth. From a practical point of view, the control of preferred orientation may often be important for the successful fabrication of metals into usable components. During the past few decades many experiments have been devoted to the study of deformation textures. This work, however, has been confined in large part to metals and alloys that have an fcc crystal lattice. By comparison, bcc metals and alloys have received much less attention, and consequently our understanding of preferred orientations in these materials is only shallow. This state of affairs worsens when it is realized that almost all of our present howledge about this class of materials derives from studies on irons and steels.' The bcc refractory metals, which are relative newcomers to the industrial world, have, on the other hand, been given at best only passing glances in the area of texture development. Our understanding of the evolution of preferred orientations in bcc metals can only remain fairly limited until systematic studies of metals and alloys other than the irons and steels have been carried out and the influence of the many variables has been determined. To that end a program was initiated to investigate in detail texture development in niobium. The present paper reports some of the results of this study. Textures were determined at both the center and surface of strips rolled variously to as much as 99.5 pct reduction in thickness at subzero temperatures. Emphasis in this paper is on texture description and on texture evolution during rolling to progressively heavier deformation. EXPERIMENTAL PROCEDURE The niobium was purchased from the Wah Chang Corp. as a 3-in.-diam electron-beam-melted billet. Chemical analysis indicated the impurities to be less than 300 ppm Ta, 40 ppm C, 10 ppm H, 170 ppm 0, and 110 ppm N. All other impurities were below the limits of detection by spectrochemical analysis. This large-grained billet was fabricated into specimen stock so that a fine-grained randomly oriented grain structure resulted. This was accomplished in three deformation steps alternated with recrystalli-zation anneals of 1 hr at 1200°C in a vacuum of low 10"6 Torr range after each deformation step. The first step was to alternately compress the billet 10 to 20 pct in each of three orthogonal directions. The second step was to compress in only two directions 90 deg apart to produce a 2-in.-sq bar. The final step was to roll this bar 50 pct to give a 1-in. by 2-in. cross section. After the final anneal, metallo-graphic examination showed the material to have an average grain size equivalent to ASTM No. 5 at 100 times (i.e., 0.065 in. diam). Specimens cut from the center and edges of this bar gave no indication of detectable preferred orientation when examined by X-ray diffraction. Samples 1.5 in. long, either 0.625 or 0.750 in. wide, and approximately 0.400 in. thick were machined from this fabricated ingot. The surfaces corresponding to the rolling planes were ground so as to be parallel. The samples were chemically polished in a solution of 60 pct nitric acid and 40 pct hydrofluoric acid (48 pct solution) prior to rolling to remove any cold work introduced in the machining operations. Rolling was accomplished with a 2-high hand-operated laboratory rolling mill that had 2.72-in.-diam rolls. Prior to operation, the rolls were polished with 600 grit paper, cleaned with acetone, and then soaked in a container of liquid nitrogen for several hours. The samples were also soaked in liquid nitrogen prior to rolling and were recooled between each pass. While some slight heating of the samples occurred during rolling, this procedure maintained the sample temperature well below 0°C at all times. The samples were rolled unidirectionally, and the rolling plane surfaces were not inverted during any phase of the operation. The draft per pass averaged between 0.010 to 0.012 in. After 96 or 97 pct reduction the draft was reduced to 0.001 to 0.002 in. per pass. Samples were rolled to various reductions in thickness between 43 and 99.5 pct.

Jan 1, 1969

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890' and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,' the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

By Carl Altstetter, Roy Adams

Measurements of enthalpy changes and transformation temperatures me reported for the fcc -hcp marten-sitic transformation in pure cobalt single and multi-variant crystals andpolycrystalline specimens. From these measurements the free-energy difference between the two phases was calculated for both heating and cooling and for repeated cycles through the transformation. For heating of single crystals the average value of enthalpy change was 113 cal per mole but on cooling it was 84 cal per mole. This difference is interpreted in terms of lattice imperfections which are introduced during transformation. A calorimeter suitable for measurement of enthalpy changes of athertnal transformations is described. COBALT exhibits an allotropic phase transformation at around 417°C' where an hcp phase (a = 2.507, c = 4.0686, c/a = 1.6228)~ stable at low temperatures transforms to an fcc phase stable up to 1495°C. The transformation has a hysteresis of about 30°C— the exact magnitude of the hysteresis depending on the number of transformation cycles, grain size, impurity content, and prior treatment.'-6 The athermal character of the transformation and surface relief due to transformation shear indicate that the transformation is martensitic. Pole mechanisms for the transformation have been discussed by Sebilleau and Bibrin, Bilby, Seeger,' and Basinski and Christian. These authors have proposed that the cooling transformation is effected by rotation of a Shockley partial dislocation around a pole dislocation with a screw component of 2a/3(111). Such a rotation would change the stacking of close-packed planes from the abcabc fcc stacking to the ababab hcp stacking sequence. This mechanism would predict a lattice correspondence of {111}fcc~~(0002~cp, have been observed. One would expect the heating transformation to occur similarly, involving dislocation movements on the (0002)hcp. However, a high density of pole dislocations and high dislocation ve- locity are required to account for microscopic observations. Furthermore, the high back stress developed on the Shockley partial dislocation as it rotates toward the sessile dislocation associated with it makes it doubtful that this is in fact the transformation mechanism. A mechanism for spontaneous nucleation of partial dislocations1*l2 seems more reasonable. If a single crystal of cobalt is cycled through the transformation but never heated above 600°C, it will remain single."13 However, if the specimen is heated through the transformation and held for a short time at or above 1000°C before cooling, the cooling transformation usually involves all four {lll}fcc habits, resulting in neighboring orientations of hcp differing by 70.5 deg. This condition is termed multivariance and has been observed by Bibring and sebilleau5 and Nelson and ~ltstetter.' The latter authors used single crystals of cobalt grown in an electron beam zone refiner. They proposed that the strongly directional cooling caused the initial cooling transformation to occur on the {lll)fcc most nearly perpendicular to the temperature gradient. Transformation shear on one set of {lll}fcc planes immobilized dislocations on the other {lll}fcc planes involved in the initial transformation. Since there is only one (0002)hcp plane orientation, the product of subsequent heating transformations could have no more than two variants—the original fcc orientation or its twin. If, however, the specimen was annealed at a high temperature, such as 1000°C, there would be relaxation of dislocations into low-energy configurations, and in the absence of a sharp temperature gradient transformation on all four (111 Ifcc planes could occur. If a dislocation mechanism is responsible for the transformation, the perfection of the lattice should affect the reversibility of the transformation. Mutual constraints of neighboring grains in polycrystalline material would inhibit dislocation movement resulting in increasingly sluggish transformation. Indeed, Nelson and Altstetter found the M, to decrease and the A, to increase in going from single crystals to multi-variant specimens to polycrystals. The effect is enhanced by decreasing the grain size of a solid specimen or a powder.6'14 Data on the free-energy difference necessary to initiate the transformation gives information about the driving force of the transformation. This is an important consideration in the understanding of the transformation mechanism. The free-energy change associated with the transformation of the hcp phase to the fcc phase at some temperature T different from the equi-

Jan 1, 1969

By J. E. Murphy

The high-purity thorium metal was prepared by the Bureau of Mines from electrolytically produced thorium alloys. The thorium-chromium and thorium-manganese alloys were separated into the component elements by vacuum distillation. Chromium and manganese impurities remaining in the thorium metal after distillation at 1,850° C were <0.005 weight-percent. Removal of volatile impurities such as aluminum, calcium, magnesium, and lead was also accomplished.

Jan 1, 1969