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By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By John F. Abel

In the debate between miners and ecologists, our industry has at last begun to get some of its story told. I have been told many times that it is hopeless to even try to get our side across. Some are sure that no one will believe us even when our cause is just. My reply would be that we have to tell the truth; again, again, and again. We will never convert a fanatic, but we must try to reach the reasonable and thinking people. I am encouraged because more of us are trying. Various mining companies here in Arizona have bought newspaper space to set forth some of the facts around our local environmental problems. The Arizona Mining Association co-sponsored a symposium in March: Mining and Ecology in the Arid Environment. The symposium program included tours arranged with local mining companies. The participants saw an acid plant, an acid leaching operation, an alluvial tailings dike, a tailings pond, a smelter, and a couple of open pit mines. This wouldn't phase you until you realized that half the visitors were ecologists, watershed and wild- life managers, and other assorted conservationists. It took a lot of guts. I am proud that we had that much confidence. As Pogo said, "We have met the enemy and they is us!" Actually, we met the enemy and they were just like us-concerned.

Jan 1, 1970

By Frank E. Woolley, John F. Elliott

Mathematical models of the transient thermal behavior of a high-temperature solution calorimeter1-3 have been developed. The thermal behavior of the calorimeter is appoxirrzated by linear lumped-parameter models, and hence is described by sets of linear ordinary differential equations with constant coefficients The response of the models to various inputs is shown to agree with the response of the real system. Application of the modeling to experimental design and analysis of data illustrates the usefulness of simple models of complex systems. The early eperiments1,2 with the high-temperature solution calorimeter indicated that the change in the temperature of the bath resulting from the addition of a solute sample to the bath involved not only the direct effect due to the solution process but also possibly a secondary effect arising from the change in coupling between the bath and the induction heating coil. Consequently, an extensive analysis of the calorimeter was carried out, and models of the transient thermal processes of the instrument were developed to aid in improving the design and interpreting the behavior of the system. This paper describes the dynamic modeling; the use of it in treating experimental results has been reported earlier.3 The high-temperature solution calorimeter was constructed to measure directly the partial molar heats of solution of solute elements in a variety of liquid metal solvents.1-3 The calorimeter consists of an induction-heated liquid metal bath into which small samples of a solute element can be dropped. The bath temperature is recorded continuously, and the change in the measured bath temperature with time, dTm = f(t), resulting from the solute addition are the raw data from which the enthalpy change caused by the addition is determined. To extract the rmodynamic results from the data, the temperature change must be compared with that resulting from calibration additions of known enthalpy change. Accordingly, it is necessary to understand the transient thermal processes arising as a result of the addition to the bath. Neither modeling nor experimentation alone could provide the required insight into the working of the calorimeter. The alternate use of both methods in conjunction greatly assisted the design of the equipment and experiments, and the interpretation of the data. THE PHYSICAL CHARACTER OF THE SYSTEM The essential parts of the calorimeter, Fig. 1, for model studies are the thermocouple, the liquid metal bath and the surrounding refractories. The system is the solvent metal bath and those refractories around it which undergo a temperature change as a result of an addition to the bath, and which determine the way the temperature of the bath responds to an input. The inputs are the combined transient thermal effects arising when an addition is made to the bath. They include the thermal effects of the addition itself and the results of changed coupling between the bath and the induction coil. The response is the variation in the measured bath temperature, dTm(t) = Tm(t) - Tm(O), from an initial steady state resulting from the inputs. It was assumed in this study that the physical properties of the various elements of the system are independent of the inputs and time, although these properties may vary as the result of changes in the composition and size of the bath during a series of additions. This separation of inputs and the system is equivalent to assuming that the system is linear, i.e., that its behavior can be described by linear differential equations with constant coefficients. Linear behavior can be expected whenever the departure of each portion of the system from its steady-state condition is small enough to cause negligible changes in the thermal properties of the materials and in the various heat-transfer coefficients. Radiative heat transfer is important in this system, so the assumption of linearity should be valid only for small temperature deviations. Several conclusions were drawn from operation of the calorimeter in earlier experimental studies: 1) Radiative heat transport from the top of the bath is a significant portion of the total heat lost from the bath. However, for small changes in the bath temperature the change in transport by this path could be assumed to be proportional to the change in the bath temperature. 2) A very small portion of the heat input is lost through the thermocouple to its water-cooled holder. The thermal resistance and thermal capacity of the thermocouple protection tube are small, so the temperature of the thermocouple should follow closely that of the bath. 3) The remainder of the total heat lost from the bath will pass by conduction through the crucible to, and through, the other refractories, eventually being absorbed by the water-cooled induction coil or by the water-cooled sides and bottom of the enclosure. 4) The thermal resistance between the bath and crucible is very small. Thus the thermal capacity of the crucible will affect the temperature of the bath very soon after an addition of heat to the bath. 5) The thermal resistance between the crucible and the silica sleeve is large, especially if a radiation shield is placed in the gap. The effect of the thermal capacity of the sleeve thus will be significant only at longer times. The thermal resistance through the packing below the crucible also is large, so the packing and the silica sleeve will have similar effects on the behavior of the system. 6) A large temperature drop exists across the gap containing the water-cooled induction coil. Thus for relatively small changes in the thermal input to the bath, the refractories beyond the sleeve

Jan 1, 1970

MR. RIGG: Gentlemen, I would like to welcome you all to the symposium this morning. My name is Jack Rigg, and I m a special assistant to Hollis Dole, Assistant Secretary of the Interior for Mineral Resources. Hollis is not in town this morning, and I am here to pinch-hit for him. The first order of business this morning is remarks by the Honorable Russell Train, Under Secretary of the Department of Interior. Mr. Train. MR. TRAIN: Thank you, Mr. Rigg. Lest you think that Hollis Dole is not interested in this symposium, let me just say that fie is flying back from Australia just to be here. He is heading up a United States delegation in Australia meeting on resource problems in the Pacific. And I believe he will be here about noon.

Jan 1, 1970

By Henry C. Meeves

The Bureau of Mines investigated the silver production potential of the Leadville (California) mining district, Lake County, Colo., in 1966-67. The mining history of the district, the ground conditions encountered in mining, and the mine-support methods used are reviewed. The drainage problem is discussed in detail. An initial objective was to establish the existence of potential silver resources minable by low-cost open-pit methods, particularly in the silver-bearing manganese halos surrounding the major deposits. The report concludes that under present conditions, development of the deposits in the area is not economically feasible; however, a pioneer rotary noncore drilling program demonstrated that this type of exploration is technically feasible. Potential reserves of silver and associated metals are estimated. Possible mining methods for recovery of the reserves are discussed. Future production possibilities from the various subareas of the district are analysed, considering optimum operating size. Consolidation of small individual holdings for unit operation is recommended. Type of operation, amount of rehabilitation, size and type of concentrating plants required, drainage and other mining problems, and metal price trends are discussed as they bear on economic feasibility of development.

Jan 1, 1970

By R. W. Michelson

The Bureau of Mines developed computerized mathematical models to estimate the economic availability of Mesabi Range taconite concentrates; these are a quality model, a cost model, and an economic availability model. The quality model evaluates metallurgical test data; the cost model determines iron unit cost from mining and processing cost data; and the economic availability model determines quantity from geologic and ore quality data. By correlating all of the physical resource quality factors and dimensional characteristics with the economic cost factors associated with producing iron ore pellets, these three models combine to establish a final relation between iron ore reserve quantities and iron unit cost.

Jan 1, 1970

Up to 19 chemical parameters were studied in flotation pulps in six Australian lead-zinc concentrators with the aim of obtaining a better understanding of the nature of, and changes in, the chemical environment. This paperdiscusses collector residuals, metal concentrations in solution, and other parameters.Collectors used in the plants studied were various xanthates, Z-200, and Aerofloats. Xanthate residuals varied in different ways in most plants. However the general trend was for residuals to be at the O· 5-2 p.p.m. level in lead flotation and O· 5 p.p.m. or less in zinc flotation.Aerofloat residuals were also variable but in the plant concerned were at a much higher level (8-10 p.p.m.) than xanthate residuals. Z-200 residuals were in the 10-20 p.p.m. range and it was found that the Z-200 added to zinc flotation was reporting in dam return water and entering lead flotation.Copper concentrations in solution were negligibly low in those plants where cyanide was not used. When cyanide was used, copper was at the 5-20 p.p.m. level and appeared to be present as Cu(CN)-2. However the hiocyanatepresent may be important. Xanthate was also present in these solutions.Zinc concentrations ranged from 0·1 to 800 p.p.m. in different plants. The general trend was for the zinc level to be highest in the grinding circuit and to drop during flotation. However there was always an increase in zinc concentration when copper sulphate was added, even tho.ugh this incre.ase was not permanent, and the increase was greater with higher copper sulphate additions.The manganese concentration also increased appreciably during copper-activation of marmatite. In some plants lead concentrations increased from 0·1 to 1 p.p.m. during activation of marmatite.Calcium concentrations (20-1200 p.p.m.) and magnesium concentrations (10-600 p.p.m.) tended to be fairly stable in each circuit.

Jan 1, 1970

By Eifu Moriyama

In 1953, Akita Plant, having a capacity of 560 tons per month, was built at Akita city by Mitsubishi Metal Mining Co., Ltd. for the purpose of treatment of the Ikuno and Akenobe Mines's zinc concentrates. Akita city, in whose neighborhood the black ore has been discovered, is located about 500 Km north of Tokyo and faced with the Japan Sea. This plant has been continuously expanded to have the capacity of 7,500 tons per month by the end of 1969. Efforts have been made to mechanize installations and to achieve continuous process. One of the characteristics of Akita Plant is the recent establishment of the residue treatment process. Many processes had been investigated, and finally commercial sulphate roasting of the residue has been carried out since 1965. At Akita Plant, special high grade electrolytic zinc, zinc alloy for die-casting (MAK brand), cadmium, cement copper and sulphur dioxide gas are produced. Sulphur dioxide gas is sent to the next door fertilizer plant to make acid. Table 1 shows production and the average assay of the electrolytic zinc and cadmium in 1969. This plant is divided into four main sections, two subsections, and residue treatment sections: Main sections are: (M-1) roasting section, (M-2) leaching and purification section, (M-3) electrolysis section, (M-4) melting and casting section,

Jan 1, 1970

By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. 'Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.'-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970

By D. Brabec

One of the analytical problems in exploration geochemistry is the choice of a method of sample attack which would be rapid, simple and reliable in terms of precision and discrimination between different concentration levels of elements sought. The wet sample attacks currently used in analysis of silicate rocks vary from total decomposition to leaching by weak extractants. The total decomposition of such materials is usually achieved either by alkaline fusion or hydrofluoric acid attack. The first method requires the use of platinum vessels which is both expensive and slow for batch operation. The second type of attack is more widely applied in rock geochemistry1, but it is still relatively slow for exploration purposes and requires extra care (especially when hydrofluoric acid is used in mixture with perchloric acid). Considerable improvement in speed can be achieved by using the sample attacks which release only part of the metal present in a rock.2,4 One of such attacks is the leaching of pulverized rocks by hot aqua regia.3 Another technique widely used in geochemical prospecting involves fusion of the samples with potassium pyrosulfate (or bisulfate) followed by an acid leach of the malt .5 One of the advantages of these techniques is the use of glassware in decomposition stage which considerably increases the analytical productivity. It should be noted that partial chemical attacks tend to extract from a rock mainly the non-silicate metal which may give results more significant for exploration purposes than the analysis for total metal.

Jan 1, 1970

By Larry Cook

During the past year the news media has come in for its share of criticism. Some of it, without doubt, is justified. Much of it, like that which has been leveled against some of the rest of us, is not. We can sympathize with the newspapers and magazines, the radio and television stations. Like the coal industry, which I represent, they are a part of the free enterprise system. They depend upon advertising for their existence, and advertisers patronize those media which reach the most people interested in their product. The various news media are therefore In avid competition for circulation. Although they do have an unquestioned influence on the public, they are primarily a reflection of the public and it is in this context that we will consider them. Granted that this reflection is sometimes a bit distorted, let us admit that any subject which does not strike a responsive chord In the public will soon be dropped by the media.

Jan 1, 1970

By W. B. Weston

To mining people who have experienced the tremendous expansion of existing operations and the development of new properties over the last several years we do not have to point out the difficulties in hiring skilled equipment operators. To those of you who have opened operations in some of the more remote places in the world this is not just a difficulty. It is an impossibility. Your only recourse has been to try and train whatever manpower has been available. Depending upon your success in training, the next problem has been to keep them. On todays modern equipment, the skill of the operator remains as the greatest single variable affecting the performance of the machine. On a blast hole drill, for example, a skilled operator will get good production footage, acceptable bit life and minimal machine downtime The unskilled operator will not only fail to get the acceptable production footage but all too frequently this failure is coupled with low bit life, high repair costs and excessive machine downtime. Even between experienced operators, on identical machines, in the same kind of material we find significant variations in performance. It is, therefore, the skill of the operator, not just his experience, which makes the difference. The problem, as presented to us by our customers, has been to find a way for the unskilled man, with minimal training, to match the performance of the most skilled and experienced operator. The obvious answer is automation.

Jan 1, 1970

By Freeman Bishop

Of all President Nixon's many legislative proposals, the one that will probably have the most far reaching effect on the mining industry will be the collecting of odds and ends of antipollution programs into the confines of a single independent Federal agency, the Environmental Protection Administration. In addition, the President is asking this Congress to approve shifting some policy and planning to the Commerce Department in an agency that will probably be known as the Oceanographic and Atmospheric Administration. This division will deal with ocean mining policy and future sources of minerals and metals.

Jan 1, 1970

By E. F. Jr. Young, H. E. Steinman, G. C. Smith

Through a progressive laboratory and pilot-plant program Jones & Laughlin Steel Corp has analyzed and corrected mine drainage pollution problems at all of its coal mines. In conducting this program, the company found no "typical" drainage discharge. Each discharge point at each mine was unique, so that varied approaches were needed to eliminate stream pollution. To illustrate the variety of these approaches, the treatment of drainage from foul, discharge points at three mines in Pennsylvania will be considered here. The flows and critical analyses of the drainage sources and treated effluents arc shown in Table I. Hydrated Lime Works at Thompson Borehole The discharge stream from the Thompson bore- hole at the Vesta No. 5 mine flowed into a small branch creek where it created a "yellowboy" deposit and affected aquatic life. Investigation indicated that hydrated lime would neutralize the acid and precipitate ferric iron without aeration. Treatment of the 150.000-gpd flow, however, created about 4000 gpd of wet sludge for which there was no nearby accumulation site. With State approval, this sludge was deposited through an unused borehole into an abandoned section of the Vesta No. 6 mine several miles away.

Jan 1, 1970

By Ralph T. Buscarello

For practical purposes, the terms "natural frequency," "resonance" and "critical speed" are synonymous. A part passing though its "critical" or "critical speed" may also be said to be "resonant" or "resonating." The vibrations of a precisely balanced part can be magnified by the structure in which it is assembled. Anyone who has driven an automobile knows that it will vibrate more at a certain speed than at others. According to the formula for centrifugal force, vibration should increase steadily with a rise in rpm. What happens instead is that the vibration not only in- creases with r m. but suddenly rises at a much higher rate through the critical speed, and then apparently smooths out as the rpm passes beyond it. To visualize what happens, consider a simple flat spring with a weight mounted at one end. When the spring is deflected by pulling down on the weight and then letting it go, the spring will oscillate, and the spring-and-weight system will vibrate at its natural frequency. If the timing or direction bf the impulses imparted to the spring did not coincide with its natural frequency, the result would be an irregular vibration that would not build up. If, on the other hand, the timing and direction of the impulses did coincide with the spring's natural frequency, the result would be a larger and larger amplitude. If the impulses were continued indefinitely, the amplitude of the spring's vibrations would go on rising [while its frequency stayed the same] until the spring broke or the amplitude of the vibrations reached an equilibrium [because frictional or other forces would tend to damp it]. Resonance magnifies the amplitude of vibrations in a relatively undamped system between 100 to 200 times over that of nonresonant vibrations. Frictional or viscous damping often reduces the magnification [from 10 to 20 times], but even with this reduction the amplitude would still be large enough to cause excessive wear, and sometimes even fractures. For example, a blower might show only 0.001 in. of vibration on the manufacturer's test stand. Installed, the blower could pass into its critical speed [the speed at which the frequency of the vibrations caused by the rotor coincides with the supporting structure's natural frequency], and the 0.001 in. of vibration could be resonated to 0.010 in., or as much as 0.020 in. The cure for such a condition would not be to lower the vibration of the blower by further balancing or better alignment but to separate the two frequencies by at least 20 to 30%.

Jan 1, 1970

By J. Lewis, J. Harper, M. F. Ashby

A grain boundary in a metal interacts with second-phase particles, which exert a pinning force (first estimated by Zener) on the boundary opposing its motion. We have computed the shape of boundaries which interact with more or less spherical second-phase particles and have constructed a soap-film model to reproduce the shape of the boundary surface. An important result is that measurement of this shape allows the pressure, or driving force, on the boundary to be measured. We hare applied this technique to grain boundaries in two alloys and hate measured the pinning force exerted by single second-phase jwrticles on the boundaries. It is in good agreement with Zener's estimate. J\. boundary between two grains, or two bulk phases, interacts with small inclusions or particles of a second phase, whether they are gas or solid. This interaction means that the boundary, forced to migrate by a difference in free energy between the material of the two grains or phases which it separates, exerts a force on a particle which it touches, tending to drag it forward. (The movement of inclusions through metals under the influence of this force, has, in fact, been observed. 1-3) Equally, the particle can be thought of as exerting a pinning force on the boundary, tending to hold it back. Zener (in a celebrated private communication4) first realized that this interaction, and the resulting pinning force, existed. His calculation of its magnitude was crude but adequate: a spherical inclusion of radius r blanks off an area nr2 of the boundary on which it sits; since the boundary has an energy of rMM x per unit area, the blanlung-olf decreases the energy of the system by MM: this energy is returned to the system if the boundary is pulled free from the inclusion— a forward movement of the boundary by a distance r will do this—so that the maximum pinning force is Trrym.M- A similar argument can be made for inter-phase boundaries. The nature of the particle itself did not enter this, or two subsequent treatments.5,6 When it is considered, tic leifthe energyoftheb a) The boundary may enter and pass through the particle if the energy of the boundary is lower within the particle than in the matrix. Fig. l(r/). Certain coherent precipitate particles behave like this. h) More usually, the boundary will bend round the particle, enveloping and bypassing it. Fig. l(b). In doing so, it changes the structure and energy of the interface between the particle and its matrix. This means that the boundary does not touch the particle surface at right angles, as early treatments assumed,5'9 but at some angle a which depends on this change in surface energy of the particle, and can be calculated from the equilibrium of surface tensions. Most precipitate particles and inclusions behave like this. Gas bubbles or liquid drops can be regarded as belonging to either group. The progress of bypassing is conveniently measured by the angle shown in Fig. 1. When the nature of the particle is ignored, its maximum pinning force is exerted when - 45 deg. When it is considered, this critical value of is found to depend on a and thus on the nature of the particle. The maximum pinning force lies between nryMM and 2jtjMM (Appendix 1). not very different from Zener's result. In reality, a boundary between crystals has a specific energy and tension which varies with the orientation of the boundary. Furthermore, recent experiments7 indicate that such a boundary is not atom-ically smooth, but has steps on it: migration of the boundary corresponds to the sweeping of these steps across the boundary surface, like the Frank model of crystal growth from the vapor. This means that the interaction of a boundary with particles should really be considered in terms of the way in which particles hinder the movement of these steps. To suppose a grain boundary or interphase boundary to be smooth, and to ignore the variation of its energy with orientation, is to liken it to a soap film. The advantage of this soap film approximation, which we have used throughout this paper, is that interaction energies and boundary shapes can be calculated easily. We have done this by numerical computation and by using a soap film model, and have compared the results with grain boundaries in an aluminum-based and a copper-based alloy. It turns out that the shape of the boundary which bulges between particles allows the pressure an it to be calculated; that is, the local driving force an the boundary can be measured. This has allowed us to check the Zener relationship experimentally.

Jan 1, 1970

By H. L. Bourne

This paper describes six basic stages between perception and production for a new sand and gravel deposit. Sand and gravel, like many of our natural resources, is taken for granted. It is assumed by John Q. Public that because sand and gravel is ubiquitous that it is available whenever and wherever needed - so long as it does not have to be mined in his neighborhood. This idea illustrates one of the enigmas of the industry, the fact that sand and gravel is abundant; however, its availability is another matter. Another problem is that this resource falls in the category of high volume, low profit materials; therefore, transportation costs are critical. Transportation roughly doubles the cost of these materials. It is not difficult to find sand and gravel, at least in Michigan. The problem is to locate a new source close to a market, near an adequate transport route (usually a highway) and in an area which will allow mining.

Jan 1, 1970

By J. Waldman, M. B. Bever, A. K. Jena

The heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of one solid solution have been measured by tin solution calorimetry. The heats of formation are analyzed in terms of the quasichemical theory. If the enthalpy diffel-ence between a hypothetical fcc form and the hcp form of cadmium is taken into account, this analysis does not lead to the conclusion put forth in the literature that electronic effects make significant contributions to the heats of formation of silver-rich Ag-Cd solid solutions. The temperature dependence of the heats of formation is appreciable and negative near 78ºK, but decreases gradually to nearly zero abore 400°K. The relative partial enthalpies per grarn -atom of silver at 541°K and cadmium at 532" and 541°K in tin have also been determined. THE composition range of the silver-rich Ag-Cd solid solutions stable at room temperature extends to about 40 at. pct Cd. Heats of formation of these solid solutions at 308" and 723°K have been measured by solution calorimetry.1,2 Heats of formation for an average temperature of 800°K have also been calculated from vapor pressures.2,3 The heats of formation deviate from the values predicted by the quasichemical theory above about 30 at. pct Cd. This deviation has been attributed to electronic effects at the Brillouin zone boundaries.2 The heats of formation of Ag-Cd alloys are essentially the same at 308", 723", and 800°K; consequently the temperature dependence of the heat of formation d?H/dT = ?Cp is vanishingly small, although from the exothermic heats of formation a negative value would have been expected. In the investigation reported here the heats of formation at 273°K of 6 silver-rich Ag-Cd solid solutions and the heat of formation at 78°K of 1 solid solution have been measured by tin solution calorimetry. The results are analyzed in terms of the quasichemical theory and the dependence of the heats of formation on temperature is discussed. The relative partial enthalpies per gram-atom of silver in tin at 541" and cadmium in tin at 532" and 541°K were obtained in the course of this investigation. The values of the temperature dependence of the relative partial enthalpies per gram-atom of silver in tin derived from the data reported by various investigators2,4-9 are contradictory. The literature contains only a value for 517°K of the relative partial enthalpy per gram-atom of solid cadmium in tin.2 EXPERIMENTAL PROCEDURES Samples of Ag-Cd solid solutions were prepared by melting weighed amounts of silver (99.99 pct pure) and cadmium (99.95 pct pure) in graphite crucibles under a flux of molten potassium chloride.10 The solidified ingots were sealed in evacuated Vycor tubes and annealed at 775°K for 10 days. The ingots were swaged and drawn into wires. The wires, sealed in evacuated Pyrex tubes, were held at 725°K for 5 hr and cooled to 365°K at an average rate of 2.5ºK per hr, followed by furnace cooling to room temperature. Chemical analysis of samples taken from different parts of each ingot gave no indication of segregation. Metallographic examination showed the samples to be homogeneous. Samples of the solid solutions or of the component elements were added to tin-rich baths in a calorimeter." At the start of a run the bath consisted of pure tin. Silver was used in the form of wire of 0.01-in. diam as supplied and cadmium in the form of lumps. Gold (99.999 pct pure) was added with the samples in order to reduce the endothermic heat effect of additions of Ag-Cd solid solutions. Samples of only one composition were added in a run and the ratio of the weight of alloy to that of gold was the same in all additions of a given run. In each run several calibrating additions of tin were made from 273°K. The heat contents of tin were calculated from the following equation, which is based on published data:12 (HTºK- H279º) = 6.70 T - 72,300/T + 20 cal/gram-atom; 505°K < T < 650°K The heat effect of each addition was plotted against the average of the sum of the atom fractions of solutes in the solution before and after that addition. The total concentration of solutes at the end of a run was less than 2 at. pct. In this range the heat effect was a linear function of the atom fraction of the solutes. The heat effect at infinite dilution and the composition dependence of the heat effect were obtained from the plots. RESULTS AND DISCUSSION Evaluation of Data. The linear dependence on composition of the heat effects of additions suggests that in the dilute range the enthalpy interaction coefficients other than the first-order coefficients of silver, cadmium, and gold are negligible, as shown in a concurrent publication.13 The heat effects at infinite dilution and the values of the composition dependence of the heat effects are listed in Table I.

Jan 1, 1970

By Alan Arias

On grinding in pure water, zirconium, tantalum, iron, and stainless-steel powders were extensively comminuted and simultaneously oxidized with hydrogen release, whereas nickel, copper, and silver powders did not react with water and their particle sizes increased. On grinding nickel, copper, and silver in water pressurized with oxygen, nickel and copper became extensively comminuted and were oxidized, whereas silver did not react with oxygen and its particle size increased. From these results and other considerations , it is hypothesized that for extensive comminution of ductile metals and alloys to occur on grinding they must react with the grinding media. UlTRAFINE metal and alloy powders are finding an ever-growing number of applications in metallurgy and in other fields.&apos; Of particular interest are ultrafine metal and alloy powders suitable for dispersion strengthening.2&apos;9 Various research programs on dispersion strengthening are being carried out and in some of these programs the ball-milling method is being used to produce dispersion-strengthened materials. This method usually involves the simultaneous grinding of metal or alloy and a dispersoid followed by consolidation of the resulting powder mixture. To obtain the ultrafine powders required for dispersion strengthening,&apos; grinding is carried out in many liquids, including aqueous and nonaqueous media, with or without grinding aids.4&apos;5 Nonaqueous liquids usually contain water as an impurity and some grinding aids may contain water of hydration.5 The water present may affect the grinding process. The writer has shown5 that. on ball milling chromium in water, the chromium is oxidized and hydrogen is released. It was surmised that the same reaction may occur on ball milling other metals and alloys in waterbearing liquids. Therefore, the investigation of ball milling in water was extended to metals and alloys other than chromium. In the course of the investigation, however, it became apparent that the data-to-gether with the results from a few additional experi-ments—could be used to postulate a comminution mechanism for ductile metals and alloys. A well-known comminution theory is that of smekal.7 According to this theory, comminution is possible because of the weakening effects of surface cracks and other imperfections in materials. This theory imposes a lower limit of about 1 µm for the ground particles. The beneficial effects of liquids and additives on the rate of grinding are well known.8 Mechanisms by which liquids and additives may aid in grinding were reviewed by Rose and Sullivan.&apos; One aspect of these effects is based on Rehbinder&apos;s theory of crack propagation in materials under stress.9 According to Reh-binder&apos;s theory, liquids or additives may promote the spread of cracks in stressed materials by lowering the surface tension at the crack tip. Rose and Sullivan surmise that the same mechanism may be operative during grinding, thereby facilitating comminution of the particles. In addition, Rose and Sullivan reviewed how additives may act as dispersants as a result of their being adsorbed on the surface of the particles being ground. This concept has been suggested by Quatinetz, Schafer, and smea15 to explain from their experiments the major role of additives that enabled them to grind metal down to 0.1 µm. Discussions of other comminution theories and additional sources of material on the subject will be found in Ref. 10. None of these previous suggestions and theories, however, can account for all phenomena encountered during ball milling of metals to submicron size in this and in a previous investigation by the author.6 The objectives of this investigation were to determine the behavior of metal powders during ball milling either in pure water or in oxygenated water and to gain an insight into the grinding mechanism. Zirconium, tantalum, iron, nickel, copper, and silver powders were ball-milled in pure water. These metals were selected because their oxides cover a wide range of free energies of formation. For comparison purposes, an alloy-type 430 stainless steel-was also ball-milled in pure water. The pressure of the hydrogen released during ball milling was monitored in order to determine the oxygen that combined with the metal or alloy. In order to obtain more information on the nature of the grinding process, nickel, copper, and silver powders were also ball-milled in oxygenated water (water pressurized with oxygen). The oxygen that reacted with the powders was determined from the pressure decrease in the mills. The powders resulting from ball milling in pure water and in oxygenated water were subjected to surface area, optical microscopy, and X-ray diffraction analyses. With these data, the oxygen calculated to be combined with the metals during ball milling, and comparison of the free energies of formation of the oxides of the milled powders with that of water, a comminution mechanism was postulated. MATERIALS, EQUIPMENT, AND PROCEDURES The materials used in this investigation were powdered metals, deaerated distilled water, high-purity helium, and commercial grade (99.5 pct purity) oxygen. The powdered metals used were zirconium, tantalum, iron, nickel, copper, and silver. A 16 pct Cr, ferritic stainless steel, type 430, was also used. The purities (or nominal compositions) and the surface areas of these metals and the alloy are given in Table I.

Jan 1, 1970

By John V. Beall

If you will be patient, we will explain how our plans to research the fishing possibilities of the Buffalo River following the SME Fall Meeting turned out, in general, to be an extension of the main theme of that meeting and, in particular, to confirm an astute observation on research made by Australian T. R. A. Davey in his Award-acceptance address at the Pb-Zn Research Luncheon. Buffalo River State Park is reached via Yellville where we tried without success to find one Odie Tollett who had been recommended as a boat liveryman. However, Mrs. Leon Dodd, in the Park, outfitted us nicely with a 17-foot aluminum canoe. Rain had dominated the recent weather of the Ozarks in northwestern Arkansas. So, under a leaden sky and intermittent showers, we stood on the bank of the turgid Buffalo demonstrating to our spouse, Sylvia, how to cast. Of course, with the water up and the sediment, the outlook for catching fish was bad. Sylvia said, however, "Oh, I get it. Let me try. Umm, like this I got one!" Sylvia reeled in a pretty ten-inch brown trout. "The poor thing, let&apos;s throw him back."

Jan 1, 1970