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By N. Jaffe, J. E. Dorn

This investigation is concerned with the possibility that the creep resistance of metals might be reduced as a result of recovery at the creep temperature when the applied stress is reduced. For this purpose the effect of stress on the recovery of the creep behavior of pure polycrys talline aluminum was investigated in the cross-slip temperature range where the activation energy for creep is 28.000 cal per mole. Before recovery all specimens were given the same substructure by creeping them under a stress of 7800psi to a strain of 0.218. Recovery was then accomplished by holding the specimens at the creep temperatures of 327" and 337°K under a series of reduced stresses for various periods of time. When the original stress was reapplied the specimens crept more rapidly than when the original stress was first removed, illustrating that recovery did take place. The extent of recovery could be indexed in terms of the UNDER certain conditions of test, the creep rate decreases over the primary stage of creep often by as much as a factor of 10~B. Since the external variables of stress and temperature are held constant, such pronounced and significant changes in the creep rate must be attributed to various substructural modifications that are introduced as a result of creep itself. At the secondary stage of creep, over which the creep rate remains constant and the substructure no longer changes, a balance must be achieved between the rate of increase in creep resistance due to creep straining and the rate of recovery of the substructural modifications. The general validity of these concepts on substructural changes has already been shown,' including the corollary that a more creep-resistant substructure is introduced under a more rapid creep rate arising from a higher applied stress.' In spite of these well-documented facts, very little progress has been additional strain undertaken by the recovered specimen to achieve the same strain rate as the unrecovered specimen. It is significant that the higher recovery stresses gave the most rapid rates of recovery. Over the high range of reduced stresses, where some creq took place during recovery, the activation energy for recovery equaled that for creep, namely 28,000 cal per mole. But for stresses during recovery below 0.80 of the original creep stress, no creep was detected during recovery and an activation energy for recovery of about 72,000 cal per mole was obtained. Whereas the activation energy of 28,000 cal per mole suggests that cross-slip of dislocations is responsible for this recovery, the mechanism for the 72,000 cal per mole process is not known. This activation energy, however, is about twice that for self-difhsion. made in determining, in satisfactory detail, precisely what substructural changes so effectively modify the creep rate.' Up to the present, electron microscopy has failed to uncover, in a satisfactory quantitative manner, the mechanistic processes involved. Since, however, creep, at least at moderate and high temperatures, arises from one or more types of dynamic recovery processes, it should be possible to shed additional light on the total problem by investigating the recovery of creep resistance. The importance of such an investigation becomes apparent when the fact is recognized that there has yet been no direct experimental proof that the rate of softening due to substructural changes as a result of recovery equals the rate of hardening due to creep-induced substructural strengthening over the secondary stages of creep. Furthermore the problem of what happens to the creep-strain induced strengthening when the material recovers either at zero or some reduced operating stress has significant engineering consequences. It was for these reasons that the present investigation on the recovery of creep behavior was initiated. Inasmuch as a substantial background has now developed on the creep of high-purity aluminum, this material was again selected for the current investigation. Furthermore extensive evidence is now

Jan 1, 1963

By P. E. Hildebrand, S. W. Mao, C. N. Crain

Hydrologic and economic criteria figure in many obvious ways in water resources development, but they are rarely linked quantitatively, and most of the applications are pertinent only to the case in point. In the preparation of a regional plan for the massive program of groundwater development in the Punjab, situations have arisen where the choice among two or more alternatives was made by analyzing the economic implications of critical hydrologic parameters. Two of these situations which are of more or less general interest are described herein. The first involves basic development policy, i.e., the question of whether groundwater development should be based on the demand of the economy, or the conservation concept of safe yield. The analysis demonstrated that mining of groundwater is clearly indicated for areas where alternative supplies are unavailable. The second problem involves integrating hydrologic data into an economic model to determine optimum well design. From an analysis of all pertinent factors, a simple nomograph was derived for determining well specifications on site during construction. The nomograph can be modified for use in any alluvial terrain. In the Northern Zone of the Indus Plains —the region known as the Punjab- Pakistan is proceeding with integrated development of water and land resources on a scale never before contemplated. The heart of the development plan is a massive program of groundwater development to supplement canal irrigation supplies and to provide drainage relief to the irrigated lands. By the close of 1966 about 2500 high-capacity wells were in operation and furnishing the water supply and drainage requirements for nearly two million irrigated acres. The development plan calls for the construction of a total of nearly 30,000 wells with an aggregate capacity of 120,000 cfs by 1980. This is part of an integrated program eventually affecting over 20 million acres of irrigated lands. [This development program is administered by the West Pakistan Water and Power Development Authority (WAPDA) for which the firm of Tipton and Kalm-bach, Inc. serves as regional planning consultant for the Northern Zone. The material presented herein is derived from planning studies which have been made in connection with the preparation of a regional development plan for the Northern zone.] Pakistan is proceeding with this large-scale development of land and water resources at a time when she is at the threshold of an almost calamitous population growth. Furthermore, she is attempting this development at a time when most of her usable land is already occupied and her food demands exceed current production. Here in the Northern Zone is one of the largest continuous areas of irrigated land in the world, easily irrigated, with a warm, dry climate and ample potential supplies of surface water and groundwater. Except for an abundance of land and labor, other primary resources are lacking or in very limited supply. The agriculture sector so dominates the economy that only by means of an effective development of the agricultural resources can other sectors grow and contribute to a viable economy. Because of inadequate irrigation, farming here has not effectively participated in the twentieth century revolution in agriculture, and only by means of massive development of potential supplies can Pakistan catch up. Capital for any kind of mass development must come from the outside. But the overriding restraint to development of the land and labor resources is the availability of water. ECONOMICS OF DEVELOPMENT The decision-making process in planning regional development becomes increasingly complex as the various sectors of the economy become more highly developed. Where, as in this case, one sector dominates the economy and its development can be considered the key to development of other sectors, the decision-making process is simplified and it is easier to identify alternatives and to trace the prob-

Jan 1, 1970

By Pradeep K. Rohatgi, Clyde M. Adams

Structures obtained on freezing of several hypo-and hypereutectic Al-Cu alloys over a range of solidification rates have been examined. Dendrite spacing, L, increases linearly with solute concentration and with the square root of the inverse freezing rate. The relationship for hypoeutectic alloys is: where rate of change of fraction solid with time, is freezing rate, C is solute concentration, (pct Cu)=1. Mass transport in inter dendritic liquid during solidification is analyzed; the experimental observations suggest maximum concentration differences and constitutional supercooling in the inter dendritic liquid increase with an increase in the solute concentration. The dendrite morphology changes with freezing rate and alloy composition. The dendrites of the a phase are parallel, uniformly spaced plates with slow freezing and rods with rapid freezing. Nonor-thogonal side branching has been observed in phases with cubic and tetragonal structures. Side branches in a dendrites are orthogonal with slow freezing and at 60 deg with rapid freezing. Formation of second-phase envelopes around the Primary phase is also discussed. DENDRITIC structure is characteristic of many types of phase transformation. The most extensively studied so far has been solidification of liquid solutions. chalmersl and coworkers have interpreted the formation of dendrites in terms of the breakdown of a planar interface. Most of the work done concerns itself with the development of an instability at the interface. Little theoretical work has been done quantitatively to relate the parameters of dendritic structure to mass transport in the liquid phase. A few empirical relations based on the experimental2'3 observations exist in the literature. Several workers2 including Brown and Adams1 have studied dendrite spacing in A1-Cu system as a function of solidification variables. In most cases, dendrite spacing has been found to increase linearly with the square root of some parameter proportional to the freezing time. The effect of solute concentration is not clear; some workers report the dendrite spacing increases with solute concentration4 whereas others report vice versa.''' ~ohatgi' has observed an increase in the spacing between ice dendrites with an increase in solute concentration in water. Tiller has also suggested that dendrite spacing should increase with solute concentration. In the present work dendrite spacing and morphology have been examined as a function of solute concentration and freezing rate. The freezing rate is defined as the fraction of liquid solidified per unit time, dfs/dß?, where f, is the fraction solid and 8 the time. The fastest freezing rate studied was 4550 times the slowest freezing rate. THEORETICAL CONSIDERATIONS It is of interest to analyze the concentration distribution in the liquid phase between growing dendrites during solidification, Fig. 1. Since this distribution is a direct consequence of the rejection of solute by the growing solid, a diffusional process, the concentration gradients increase with the freezing rate. However, when solidification rate is the only variable in a series of experiments, the interdendritic liquid regions become smaller (i.e., the dendrites become more closely spaced) with an increase in freezing rate. The main purpose of the analytical treatment of interdendritic liquid diffusion will be to reveal a tendency for dendrite spacing to decrease with increasing solidification rate in just such a way that the maximum concentration differences developed in the liquid phase are remarkably independent of freezing rate. Two rather different analyses are set forth, one pertaining to the one-dimensional diffusion which obtains in the interdendritic liquid between parallel plate-shaped dendrites, and the other to the cylindrically symmetrical diffusion around rod-shaped dendrites during early stages of solidification. The results of the two analyses are quantitatively similar, correlating dendrite spacing, maximum concentration difference, and freezing rate. First consider the simpler one-dimensional case. Two parallel plate-shaped dendrites are separated by a distance, L, between centers, Fig. 1. Solidification takes place by the thickening of these plates, with solute being rejected into the liquid. It is assumed there is no diffusion in the solid. This thickening process is slow enough and the dendrite spacing small enough that the concentration differences which develop, although interesting and important, are very small (an important assumption which is verified ex-

Jan 1, 1968

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By D. C. Seidel, E. F. Fitzhugh

The Colorado School of Mines Research Foundation has developed a hydrometallurgical process for recovering nickel from oxidized ores, including both the iron-rich laterites and magnesium-rich, soft silicates. Known as the HSO-HTCP (Hydrothermal Sulfidization Oxidation-High Temperature Cementation in Pulp) Process, the system consists of feed preparation, sulfidization, oxidation, precipitation (cementation), and calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Nickel sulfide ores lend themselves readily to concentration before smelting or pressure leaching, but neither of the major oxidized ore types — the iron-rich laterites and magnesium-rich, soft silicates-has been directly concentrated. Upgrading of crude ore in current practice is limited to cobbing lumps of the harder, lower grade rock (protore) from the softer, enriched silicate ore, because only a small percentage of the nickel in these ores occurs in discrete, contrasting mineral particles. There is no apparent mineralogical contrast in the superficial, iron-rich lateritic ores and, in fact, there is no firm assurance that the nickel atoms are within the lattices of the limonite minerals, or else irregularly adsorbed on the limonite. Within underlying, "rotten rock" silicates, occasional veinlets of gamierite and related nickeliferous silicates are found.' The gamierite veinlets, however, are only incidental, and the majority of the nickel atoms occur as erratic replacements of magnesium atoms in the micaceous chlorites of the ore mass. Pyrometallurgical processes account for nearly all the nickel currently being recovered from oxidized ores. Plants in New Caledonia, Oregon, Japan, Brazil and Greece smelt the ores to make ferronickels or a sulfide matte,2 and the ammoniacal leaching3 at Nicaro, Cuba, is preceded by a reducing roasL4 The only fully hydrometallurgical installation has been the politically ill-fated Freeport Nickel Co. enterprise, and this process was limited to lateritic ores.5p6 A hydrometallurgical technique which might handle both laterite and the typically richer silicate ores has been an enticing goal. The technique described here was developed at the Colorado School of Mines Research Foundation, Inc. on behalf of the Republic Steel Corp. It uses sulfur, heat, air and metallic iron to recover nickel from these ores. Inasmuch as the ores are treated as aqueous slurries, the cost of drying a plant feed that normally carried 30% or more moisture is eliminated, and there are no dust problems. Patent applications have been filed by Republic Steel Corp. on the procedures used for getting the metal into solution and on the subsequent recovery without liquids-so l ids separation of the slurry. It is referred to as the HSO-HTCP Process (Hydrothermal Sulfidization Oxidation — High Temperature Cementation in Pulp). THE PROCESS FLOWSHEET The results of various experimental studies have been combined to form the continuous flowsheet illustrated in Fig. 1. This flowsheet serves as a general pattern showing the sequence of the operations which include: (1) feed preparation; (2) sulfidization; (3) oxidation; (4) precipitation (cementation); and (5) calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Feed preparation: In general, the silicate ores can be considered as earthy rather than hard, and preparation might be carried out before the addition of water in a trommel, or with water in a scrubber or log washer. This breaks up the earthy particles, allowing the hard lumps to be separated by screening. The oversize material from most ores is relatively barren and may be discarded. If there is occasion to control the iron-magnesium ratio in the plant feed, laterite, which normally breaks up readily into fine sized particles, and silicates are mixed in suitable proportions. The fine product slurry from the initial steps is mixed with elemental sulfur and fed to a conventional ball mill, although the amount of actual grinding that takes place is relatively small. The object of milling is to complete the disintegration to natural particle size and to produce an intimate mixture of the ore and elemental sulfur. This pulp, which is almost entirely -200 mesh, has a pH of about 7.0 and normally can

Jan 1, 1969

By U. F. Kocks

The flow stress in some latent slip systems of aluminum and silver crystals after various deformations in single slip was investigated by transverse compression and supplemented by experiments on overshoot of the compression axis and the stability of corner orientations. Work hardening was found to be remarkably isotropic, the ratio of the flow stress in the latent system to that in the primary system being between 1.0 and 1.3. The strain-rate dependence was not significantly larger in the latent system. This low anisotropy suggests that specific dislocation interactions are not the direct cause of work hardening. Either the obstacles are essentially impenetrable so that only their distance enters, or a fairly random distribution of dislocations of all systems is. in fact. formed during single slip. The latter seems to he excluded by the observations on the strain-mte dependence and on the amount of secondary strain. The amount of seconzdary strains occurring in single slip was determined by shape-change mensurements and by a new method connected with the latent-hardening experiments. It is definitely less than 1/300 times the strain in the primary svstem. WORK hardening is due to dislocation interactions; this is a hypothesis, and possibly the only one, on which all present work-harden ing theories agree. About a dozen specific interactions have been considered, and it is unlikely that any essential one has been missed. Different work-hardening theories differ to a large extent in the specific interactions which are deemed most important. The presence or absence of any particular interaction, and its degree, depend on the geometrical relationships between the two dislocations interacting. Let us enumerate some examples. Two dislocations may react, with a varying reaction energy, to form a third dislocation, and this reaction product may be sessile or glissile. Two dislocations may intersect and a jog may be formed on both, on one of them, or on neither; this jog may be sessile17Z or glissile and it may, if moved nonconservatively, lead to the production of vacancies or interstitials. Finally, a dislocation may bypass another one and thus interact only with its stress field. All these interactions depend on the specific relation between the Burgers vectors and line directions of the two dislocations. Any dislocation generated during plastic deformation of fcc crystals belongs to one of twelve slip systems. Taking any one dislocation, its relationship to each of the other eleven can fall, by symmetry, into one of only five classes. These relationships are enumerated in Fig. 1 and Table I. Each slip system is represented in the stereo-graphic projection by two triangles, namely those in one of which the specimen axis would have to lie if the specimen were to deform in single slip on this slip system in a given sense, in a tension test. Let us represent the primary slip system by the shaded triangles. The other slip systems are classified only with respect to their relationship to this primary system. The code letters (initials of established names* in German) are explained in Table I. Three specific interactions are also listed in cases where they may be strong: the product of a reaction, the formation of jogs in either system, and the elastic bypass stress. The last column relates to the types of experiments reported in this paper and summarizes their results. To decide experimentally between the relative importance of the various interactions one would like to produce a group of dislocations in one slip system and then measure the stress necessary to force another group of dislocations of a specific second system through them. Hopefully, one can produce the first set of dislocations by plastically deforming the specimen in single slip. Then one can try to achieve single slip in a specific, previously latent system and measure its flow stress. If it is different from the virgin flow stress, there has been "latent hardening". Some types of latent-hardening experiments will be discussed in the next section. The strain-rate and temperature dependence of the flow stress is an indication of the importance of dislocation intersections. By extending an investigation of this dependence to the latent systems, one can determine how much more important forest contributions are here. seeger3 has used the as-

Jan 1, 1964

By L. A. Wilson, P. J. Root

The relative costs of heating a reservoir by steam injection and by combustion have been examined. The comparison was based on a model similar to that proposed by Chu.' The cost of boiler feed water, the price of fuel, pressure and plant capacity were parameters in determin-ing the costs of air compression and steam generation. The analyses compare the cost of heating to the same radius by the two methods. Results suggest that the two primary factors for comparison are the price of fuel and the amount of crude burned during underground combustion. The cost of fuel has a greater effect on the cost of heat from steam than it does on its cost by combustion. As a result, analyses indicate that when the price of fuel is low, steam may be unequivocally cheaper than air. The influence of heat loss is such, however, that as the heated radius increases combustion becomes relatively more competitive depending upon the amount of crude burned. This implies that steam may be cheaper for small stimulation jobs (huff and puff) but combustion may be more economically attractive for heating large areas (flooding). INTRODUCTION Use of thermal methods of recovery is an accepted fact today. After an induction period of several years, processes are being widely used that involve reservoir heating to augment recovery. Of the several techniques, steam injection and forward combustion appear to be destined to dominate the field. Although the objectives of both are the same, the basic differences between generating heat in situ and injecting heat after surface generation influence the cost in different ways. This study compares the cost of heating a reservoir either by steam injection or by forward combustion. There has been no consideration of recovery. Presumably, recovery from the swept region would be high in either case. The sole consideration was the cost of heating to the same radial distance by either process. PROCEDURE THE MODEL The basis for comparison was a mathematical model similar to that used by Chu' for combustion. The model simulates a radial heat wave in two-dimensional cylindricaI coordinates. It includes heat generation, conduction and convection within the reservoir and conduction in the bounding formations. Thus, heat losses from the formation are considered. Three significant modifications were made. 1. Equal logarithmic increments rather than equal increments were used for the mesh spacing in the r direction. By this technique large distances were simulated with relatively few mesh spaces. 2. A backward difference approximation to the convection term was used to avoid troublesome oscillations which result from a central difference approximation when the convection term is large. 3. The radial increments of the combustion zone motion were not necessarily uniquely related to the mesh configuration. The cumbersome step function introduced by the heat of vaporization of steam was circumvented by assuming the enthalpy of the steam to be a linear function of temperature between reservoir temperature and steam temperature. This is equivalent to assuming an average heat capacity numerically equal to the difference between the enthalpy of saturated steam and the enthalpy of water at reservoir temperature divided by the difference between the two temperatures. Heat losses obtained by this model are in essential agreement with those obtained by the analytical solution of Rubenshtein.' A detailed description of the model is presented in the Appendix. Using the model, the times required to heat to particular radial distances were obtained as a function of injection rate and other physical parameters. For the steam case, injected fluid was assumed to be saturated steam at pressures of either 500, 1,000 or 1,500 psia. The corresponding temperatures are 467, 544 and 596F, respectively. Thickness ranged from 10 to 50 ft and injection rate ranged from 100,000 to 1 million Ib/D. Reservoir and overburden temperatures at the injection well were assumed to be that of saturated steam at the injection pressure. The effect of maintaining the overburden temperature at the well at a different temperature (initial reservoir temperature) was examined with no significant change in behavior. The influence of wellbore heat losses for the steam case was determined in the following manner. The rates of heat loss as a function of time were estimated using an approach similar to that suggested by Ramey." he data were based on injection through 2%-in. tubing in 7-in. casing. Integration of these data over the entire iniection period yielded the total heat loss. Total heat losses were then corrected to their equivalents in steam (this number resulted from dividing the total heat loss by the latent heat). This was considered additional steam required to accomplish the reservoir heating and the total cost was increased accordingly.

Jan 1, 1967

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metallurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each temperature from room temperature to fusion temperature, and cooled at a rate that is not generally controllable but is predetermined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each temperature zone. The nature of the zones produced by other types of welding is the sane. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and disadvantages of the extent of the zone are of prime moment, and are discussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known. GENERAL METHOD The scheme of procedure in the work herein reported involved the testing of the metal of each temperature zone adjacent to the weld in so

Jan 1, 1935

By Frank Harwood Riddle

Products made from the ores of the sillimanite group, and synthetic substitutes for them, have unique properties, and service tests prove that they are playing, and will continue to play, a major part in improvements in metallurgical processes. Also, they are examples of how comparatively useless, rare, or "museum" minerals have been made available in commercial quantities. Until research developed uses for them, the minerals had been observed only in small, scattered masses, or crystals. Improvements in ceramic processes and compositions have come about very gradually. In the last 10 or 15 years, several outstanding developments have been made. Of greatest interest to the mining and metallurgical engineers are those affecting the composition, necessitating the mining of new minerals, and improvements in ceramic products used in metallurgical processes. Sillimanite and Mullite Sillimanite (Al2O3.SiO2), then known as Fibrolite, according to Dana,' was first reported in 1792. In 1796, cyanite (Al2O3.SiO2) was first described.2 In 1873, Behrens published results of his microscopic study8 of porcelain. He showed that it contained what appeared to be crystals, which dissolved less readily than quartz and glass in hydrofluoric acid. Hussak4 described the presence of needlelike crystals as occurring in some instances in small amounts in certain porcelains. In 1908, Plenske and Zoellner both studied porcelain structure.5 Plenske observed that "sillimanite" might be present in masses of exceedingly minute grains which apparently were amorphous. Zoellner advanced the theory that the needlelike crystals were formed by a molecular change in the clay,

Jan 1, 1932

By John H. G. Monypenny

The range of chromium content of stainless steel is, in most cases, included in the limits 11 to 14 per cent., or the middle part of the range, 9 to 16 per cent., specified by the discoverer. For some time after the steel was produced commercially, the carbon content was about 0.3 to 0.4 per cent. and occasionally higher; only rarely was material with 0.25 per cent. carbon or less produced. The reason for this is obvious from the nature of the alloys of chromium available for making such steels; as the lowest carbon content generally available was about 1 per cent., and this in conjunction with a chromium content of about 60 per cent., the production of a 12-per cent. chromium steel with less than 0.25 to 0.30 per cent. carbon was impossible. The advent, on a reasonable commercial scale, of carbonless ferrochromium has modified this condition, however, so that for the last three years stainless material containing 0.1 per cent. or less carbon and the normal amount of chromium has been on the market. As far as the author is aware, the material was first made on a commercial scale by the firm with which he is associated in June, 1920, when a 5- or 6-ton cast of material containing 0.07 per cent. carbon and 11.7 per cent. chromium was made and cast into 12-in. ingots. The necessity for using a totally different raw material, carbonless ferrochromium, instead of the ordinary low-carbon ferro (0.6 to 1.0 per cent. carbon) has led to the idea that stainless iron is a quite distinct product and quite different from stainless steel. While this may be true from a commercial aspect, it is wrong metallurgically. The name stainless iron is unfortunate as the material is a very mild stainless steel and forms the lowest carbon member of a series of steels of continuously varying content which are, in many respccts, the counterpart of the series of ordinary carbon steels ranging from "dead soft" to tool steels. In an article on stainless steel in the Journal of the Society of Chemical Industry, November, 1920, the author said "Just as in the far-off days 'steel' was regarded as a hard product of iron, and little or no attempt was made to grade it into harder or softer varieties, so at present stainless

Jan 1, 1924

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Manuel Eissler

The material presented in this paper is an abstract of a thesis submitted by the writer to the faculty of the Massachusetts Institute of Technology, as part requirement for the degree of Master of Science. The investigation was undertaken at the suggestion of Prof. H. 0. Hofman, and it was conducted, under his direction, in the laboratories of the Mining Department of the Institute. The purpose of the work was, first, to study some of the reactions that have been considered as a part of the mechanism of the chloridiz-ing roast, and second, to study the conditions under which nickel oxide and copper oxide may be chloridized. While the production of chlorine gas by various reactions during the chloridizing roast may not be primarily useful in the chloridation of metal oxides and compounds, it nevertheless serves a useful purpose in preventing the dissociation and decomposition of chlorides once they have been formed; for example, the dissociation of cupric chloride into cuprous chloride and chlorine. Therefore it was thought that a study of some chlorine-producing reactions would prove of interest, and the first series of experiments dealt with this phase of the subject. he object of the latter part of the work was to show the possibility of treating heavy sulphide ores, such as those of Sudbury, Ontario, containing much iron and small amounts of copper and nickel, by chloridizing and removing the copper, leaving an iron-nickel oxide product suitable for smelting in the blast furnace for nickel-bearing pig iron. The chloridizing of the copper would, of course, be preceded by a roast for the removal of sulphur, the sulphur oxides being available for the manufacture of sulphuric acid, if under the local conditions this product would be of commercial value. Reactions of the Chloridizing Roast Reaction of Sodium Chloride, Sulphur Trioxide, and Oxygen.—The first reaction studied was that involving the production of chlorine

Jan 1, 1915

By Alden B. Greninger, Alexander R. Troiano

Metallurgists have long believed that martensite in steel forms as plates along the octahedral {111} planes of austenite. Much has been written about mechanisms whereby units of the austenite lattice are pictured as transforming to martensite by shearing movements initiated along the octahedral planes of austenite, supposedly resulting in plates of martensite lying parallel to these planes of shear. A critical inspection of two or three photomicrographs of quenched hypereutectoid steel led us to the conclusion that the orientation habit of martensite, at least in hypereutectoid austenite, could not possibly be octahedral. Inasmuch as recent studies,30,31 of the martensite-type reaction in nonferrous alloy systems have established the irrational orientation habit as characteristic of this type of lattice transformation, the need for a thorough restudy of the crystallography of martensite formation in steel was evident. The present paper reports the results of such a study, extended to include both cementite and some of the products of constant-temperature decomposition of austenite. Also reported are a few of the results obtained from a microscopic and X-ray study of the austempering process in very high-carbon steel. I. The Martensite Transformation Previous Work Microstructure and Crystal Structure of Martensite.—Among the best series of published photomicrographs of quenched steels are those of Whitely,1 Robertson,2 Hanemann and Schrader,3 and Lucas.4 The crystal structure of martensite is body-centered tetragonal, with axial ratio varying from 1 near 0.0 per cent carbon to 1.08 for 1.75 per cent

Jan 1, 1940

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-' the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:' and, if some simplifying assumptions about particle shape are allowed, the total number of particles.'2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.' Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

By W. K. Godfrey

The highest compressive strength cement has the highest bond strength in tests in which the cement is subjected to a confining pressure. After perforating, the bond strength is reduced to nearly zero when the pipe is supported by weak cement. Perforating does not affect the bond strength, however, when the pipe is supported by strong cement. Pipe supported by weak cement is damaged by perforating with expendable capsule jets, but is not damaged by perforating with the hollow carrier gun. High strength cements are recommended for oil wells that are to be perforated. Introduction The purpose of this work is to determine the effect of jet perforating on the bonding strength of oilwell cement at simulated down-hole conditions. Bond strength is a good criterion for determining the effectiveness of cement in performing its main function, i.e., that of isolating zones. According to the literature on the subject, the optimum cement strength for perforating is low and should not exceed 2,000 psi compressive strength. This conclusion was based on the appearance of bullet and jet perforations in neat and gel cements largely done in the absence of a confining pressure more than 15 years ago. Discussion Literature A relatively weak cement has been recommended in the literature as having optimum properties for perforating. In 1947, Oliphant and Farris tested bullet perforating of neat cements at various curing times.' Some of the tests were made at down-hole conditions. They reported that the optimum cement strength for perforating was about 2,000 psi compressive strength. Enlarged holes occurred when strength was too low, and the cement shattered and cracked when the strength was too high. In 1951, Morgan and Dumbauld tested bullet and jet perforating of neat and gel cements at surface conditions.' They reported that optimum cement has a compressive strength less than 2,000 psi. In their tests at atmospheric pressure, high strength cement shattered and cracked when perforated. Thus, the optimum cement strength was based on the appearance of neat and gel cement after perforating. In 1953, Clark showed a relation between cement strength and fluid shutoff.' He concluded that a 500 psi compressive strength is required for good fluid shutoff and that maximum bonding ability is developed at approximately 1,000 psi compressive strength. In 1964, Bell and Shore invalidated most of the conclu sions by the previous authors when they demonstrated that atmospheric pressure tests cannot be used to determine casing deformation and damage that will result from perforating under down-hole conditions.' They showed that the higher the hydrostatic pressure, the more restricted will be the expansion of gases generated by the charge. Less casing deformation and damage occurs under down-hole conditions than at atmospheric pressure. In recent work, Bearden et al. reported that jet perforating at surface pressure with the hollow carrier gun caused the cement sheath to shatter and crack.' The perforating, however, did not seriously affect the pressure required to leak past the casing cement bond. Only three cementing mixtures were tested, and presumably they had strengths in excess of 2.000 psi. Bearden et al. also reported that the hydraulic bonding strength increased as the compressive strength increased. Their hydraulic test showed that approximately 1,000 psi pressure is sufficient to break the casing cement bond for a well aged neat Portland cement sheath. Unfortunately, the tests were not run with a confining pressure, so Bearden et al. were merely measuring the strength of their outer 8%-in. casing. In our investigation, we measured the hydraulic bond strength of cement to pipe under a confining pressure and found that the bond strength was not limited to 1,000 psi. Cement Bond The bond strength is a good criterion for measuring the effectiveness of cement in performing its main function, that of preventing interzonal communication of fluids behind the casing. Measuring bond strength after perforating should be a good quantitative method of determining optimum cement properties, and should be a better method than that used by previous investigators,11 ' who simply observed the appearance of the cement after perforating.

Jan 1, 1969

By W. C. Hellyer, R. A. Campbell

In single-stage autogenous grinding, the buildup of a critical size fraction in the media can be corrected by removing this material through pebble ports, crushing it below the critical size range, and recycling the crusher product back to the mill. The rate at which the critical sire fraction is crushed affects the size distribution of the grinding media and this in turn affects the sire distribution of the grate discharge. This provides a means for controlling the grind produced by a single-stage autogenous grinding unit. The pilot-plant investigations on a very hard copper ore were carried out at the facilities of the Institute of Mineral Research, Michigan Technological University. In an autogenous grinding circuit in which feed at approximately 9 in. top size is reduced to a size suitable for subsequent processing, the build-up of a "critical size" fraction in the media causes problems. A "critical size" fraction has been defined as, "media too small to effect reduction by impact grinding of ore coarser than a quarter of an inch and too large to be broken by the largest size of media in the charge."' The buildup of a critical size fraction reduces the capacity of the mill, increases the grinding power requirements per ton of finished product, and generally produces a finer grind than is desired. It is general practice to overcome this problem by the addition of large-diameter steel balls to the grinding charge. This has certain disadvantages, such as 1) an increase in mill liner wear, 2) wear on the steel balls, and 3) some loss in flexibility in grinding circuit opera-tions resulting from difficulties in removing the steel balls by means other than by grinding out. A number of investigators' have suggested the use of a small crusher as an alternative to the use of large steel balls for control of a critical size fraction. With this technique the critical size fraction is removed from the mill continuously through suitable-sized pebble ports, crushed below the critical size range, and returned to the mill. An external crusher would cause no increase in mill liner wear, the wear on the crusher would be less expensive than the wear on the steel balls, and the flexibility of the grinding circuit operations would be enhanced since the crusher can be cut into and out of the circuit at will. This paper describes an autogenous grinding pilot plant investigation on a very hard copper ore, which led to the selection of an autogenous grinding flowsheet incorporating a crusher in the circuit as the preferred method for grinding this ore. Further development of the technique demonstrated that the crusher could be employed to control the product produced by an autogenous grinding unit. Description of Pilot Plant These investigations were carried out at the pilot-plant facilities of the Institute of Mineral Research, Michigan Technological University, Houghton, Mich. The autogenous grinding unit was a 6-ft-diam by 2-ft-long Hardinge Cascade mill with %-in. slotted steel grates. Pebble ports cut into the grates allowed passage of pebbles having a top size of approximately 21/2 in. The grate and pebble-port discharge material passed over a 3/16-in, trommel screen with the trommel under -size being pumped to the classification device. DSM screens were employed for classification in the early investigations, but were replaced later by a small Dorr rake classifier. The trommel oversize material returned to the mill via scissor conveyors. When the crusher was incorporated into the circuit, the trommel oversize material passed to a double-deck vibrating screen fitted with 2-in. and 3/4-in. square mesh screen cloths. The $ 2-in. and the —2 +3/4-in. size fractions were combined and crushed to a nominal 1 in. in a 4 x 6-in. jaw crusher. The crusher discharge and the —3/4-in. screen undersize returned to the mill. In the final investigation, a flap gate fitted to the top deck of the screen directed the — 21/2 +2-in. size fraction to the crusher or back to the grinding mill. The flap gate operated manually on a 15-min cycle, with this material being crushed for so many minutes out of each cycle. This was found to be a more reliable method of controlling the amount of — 21/2 +2-in. material crushed than attempting to make a split of a small weight of material on a continuous basis. Operational Techniques: Each sample was sized into three fractions and the Cascade mill feed was reconstituted from these size fractions in the proportions existing in the original sample. Sufficient feed for 15 min operation was weighed out and fed by hand over a 15-min period. The gross mill power draft was recorded every 15 min, corrected for tare power and drive efficiency, and reported as net kilowatt-hours per ton. A recording kilo-watt-hour meter provided a continuous visual record of the power drawn by the mill. Pulp densities of the trommel undersize and the classifier overflow (or DSM undersize) were taken every 15 min. The classifier overflow was sampled automatically. Timed samples of the classifier sands were taken every 15 or 30 min, weighed, and returned to the circuit. After correcting for moisture content, the weights were converted into percent circulating load. Timed samples of the +2 in., the —2 + 3/4-in., —3/4-in. screen fractions, and the crusher discharge, were

Jan 1, 1971