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By Edgar T. Wherry

EDGAR .T. WHERRY,* Washington, D. C. (communication to the Secretary ?).-Dr. Pogue's presentation of the facts concerning the emerald deposits is very clear and convincing, and the only addition that I can suggest is a summary of previous theories of origin. He makes it evident that the pegmatite theory is the only one capable of explaining the existing relations, but upon certain details there may be some difference of opinion. If I understand the term pneumatolytic, it does not imply that all the elements concerned in a given deposit were transported as gases, but rather that the crystallization of these elements into the various minerals was favored by the presence of certain gaseous substances, notably H20, C02 and HF. It is highly improbable that the oxides of glucinum, aluminum, chromium, and silicon, which enter into the composition of the mineral emerald could have been transported in the gaseous form. The same is true of the metallic constituents of the parisite and other associated minerals. The explanation suggested, that solutions separated into liquid and gaseous portions, the latter ascending and forming the emerald in the upper portions of the rock only, therefore, seems to me untenable. When two formations exist side by side and one, A, is mineralized while the other, B, is barren, the possible explanations may he classed as (1) chemical, and (2) physical. 1. Some chemical feature of A not found in B might have caused crystallization of certain minerals in the former, which did not appear in the latter. In the present instance both rocks appear to be so similar chemically that no such effect can be looked for. Pogue mentions carbon as a possible precipitating agent, but describes both formations as carbonaceous, so that the difference in the minerals of the two can not be thus explained.

Jan 10, 1916

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By William A. Edmiston, R. E. Grace

A simplified model for the theory of reaction rates near equilibrium has been applied to the reduction of wustite. A linear relationship between the net rate of reaction and the Gibbs free-energy change, ?F, is predicted. The reduction of wustite in H2 -H2O gas mixtures was studied with a microbalance technique at temperatures from 850° to 950 °C. The predicted model was found to be valid to -?F/RT = 0.1 or approximately -200 cal per mole away from equilibrium. ThE theory of reaction rates near equilibrium has been developed by a number of authors. Prigogine, Outer, and Herbo1 have studied the catalytic hydrogena tion of benzene in an attempt to deduce some intrinsic connection between reaction rates near equilibrium and thermodynamics. Manes, Hofer, and weller2 have derived more general expressions for reaction rates near equilibrium from classical thermodynamics. Hollingsworth3,4 has commented briefly on the work of Manes et al. Benson5 has summarized in a general way the results of the earlier contributions. It is the purpose of this paper to apply the theory of reaction rates near equilibrium specifically to the reduction of wustite in H2-H2O gas mixtures. The basic premise is that the reduction of wustite proceeds by a surface reaction, rather than by solid-state diffusion ,or gaseous diffusion. Richardson and Dancy6 and Gellner and Richardson7 have suggested that the reduction of wustite may be governed by iron diffusion in wustite. Mckewan8-11 has proposed that reduced iron layers on various oxides are sufficiently porous to offer a negligible impedance to the reducing gas. The linear motion of interfaces reported by McKewan and discussed by Themelis and Gauvin12 indicates the lack of diffusive control during reduction. The reduction studies of magnetite reported by Quets, Wadsworth, and Lewis13 give additional evidence that reduction rates are linear when the reaction products are porous and nonprotective. The interpretation of measurements reported in this paper is predicated upon a surface-controlled reduction reaction, at least in the earliest stages of reduction when the reduced iron layer is thin.

Jan 1, 1967

By Peter A. Allen

INTRODUCTION Lac Minerals Ltd., a significant North American producer of gold and other metals for over three decades, recently completed the financing for its third discovery in an eight year period. From 1975 to 1982, three important gold deposits in Quebec and Ontario: namely Bousquet, Doyon and Hemlo, were located and tested by company geologists. When current development plans are complete, Lac will have injected $400 million into these deposits. A discussion of these projects and their financing reveals some extraordinary challenges faced by top mining management. Responses to these challenges developed by Lac management may interest executives planning to proceed with new North American gold or base metal mines. MINE DE BOUSQUET In 1976, we explored a property containing a large low grade surface gold deposit. The geologial setting was exciting and we tested recent rethinking about the volcanigenic genesis of gold and base metal occurrences. These ideas helped pus to persist in drilling a nearby conductor and 600,000 ton, 0.22 ounce/ton orebody was outlined. With gold at $Cdn.150 per ounce the feasibility was approved and work started February 1978. Availability of a company custom mill 35 miles away reduced our immediate capital needs to $8.5 million. First of all, understanding the geological significance of results at Bousquet was critical. Mine and surface exploration geologists at Lac are continually and closely working together to better understand the nature of gold deposits in the Shield. This management emphasis on both pure and mine geology meant that a much larger ore reserve could confidently be predicted. (A proposal to quickly develop and ship the ore to a nearby company mine was discarded.) Instead of designing just for the initial plan of 500 tons per day we therefore included headframe, shaft and hoisting capacity for 1,700 tons and provided a compartment for future shaft deepening. These prebuilt additions were welcomed within two years. The type of collaboration whereby surface and mine geologists make study and field projects of each other's problems sets the foundation for this predictive ability. At Lac, the traditional responsibility for and supervision of the mine geologist by the mine manager is modified by this collaboration. This adds interest and scope to the geologist's work and lets him think beyond production requirements. Besides such management considerations, dedicated, professional geologists with integrity and lots of practical experience are needed to plan successful developments like Bousquet. Second, projecting future bullion revenue was critical and our experience selling production for future delivery gave us a way to ensure that loan repayment at term would not be jeopardized by falling metal prices. Output from a single mine is often reduced or curtailed for numerous reasons, so "selling forward" is done best and with least risk by companies like Lac with more than one or two producing locations for that metal. At first, a forward marketing program was considered unwise, speculative and unorthodox by analysts and other producers. Declining markets in the early 1980s prolonged gold project capital recoveries however, and critics were better able to appreciate the usefulness of such a tool. The notion that gold miners shouldn't sell forward is rooted in the belief that long-run gold prices will rise as modern social theory implementation in democracies inevitably erodes currency values. Selling against this trend goes against this industry belief or "ethic" and is at odds with the company shareholder who expects the gold price to rise not fall. Nonetheless, an efficient tool is available to the gold producer (not to most other metal producers) to quickly disengage from adverse price trends or to lock in spot prices instantaneously for two years or more of profits. Gold had recently retreated from U.S.$200 to $104 and now had reversed to $150. Lac had been forced to close several of its producers during the late 1960s because central bank-controlled

Jan 1, 1985

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By W. W. Anderson

WEBSTER'S dictionary gives the following definition for "efficiency": "Effective operation as measured by a comparison of actual and possible results." Engineers think of this definition in terms of the ratio of output to input, and since they learn early in their careers that output cannot be greater than input, they usually consider a machine to be 100 pct efficient if it operates perfectly, and to be 0 pct efficient if it performs no function at all. Hence, values of efficiency between 0 and 100 pct reflect how well or how poorly a machine has performed; and any method of calculation for determining efficiency that does not show 0 pct when no function has been performed, and 100 pct when a perfect job has been done, is looked upon with skepticism. The literature on performance of coal cleaning equipment contains many references to efficiency of performance, but there is no unanimous agreement among the authors as to how the efficiency should be determined. Numerous methods of calculation have been proposed from time to time, most of which attempt to fulfill the definition of efficiency by comparing output to input, using float and sink data or some other characteristic, such as dry ash content, as a measure. However, to the best of our knowledge, none of the methods advocated in the past meets the requirements of a practical engineer in judging cleaning plant performance, because the formulas previously advocated do not confine numerical values of efficiency between 0 and 100 pct, and the literature does not contain an explanation of the meaning of the formulas under various conditions of operation. Therefore, the following formula, based on Yancey's concept of misplaced material,' is proposed as a measure of efficiency which will conform with the requirement that the values of efficiency must be confined between 0 and 100 pct: Quantitative Efficiency = 100.0 — (pct wt sink* in cleaned coal + pct wt float* in refuse)t • At gravity of separation effected by cleaning equipment. t Total product basis of the size of material under study. It will be noted from this formula that an actual separation between cleaned coal and refuse must be effected by the cleaning equipment before the formula can be used; also, that improperly distributed material in the products must be determined at the gravity of separation, rather than at some arbitrary test gravity. It will further be noted from this formula that the weight of cleaned coal recovered and the weight of refuse rejected by the equipment have their proper influence, because the sink in the cleaned coal and the float in the refuse are expressed in the equation as a per cent weight of the total products of a definite size discharged from the plant. This formula has one other important characteristic, in that it requires no knowledge of the feed to the cleaning unit. Comparison of data on the products from a cleaning unit with the feed to the unit can lead to many worthwhile conclusions. but not in regard to the efficiency of separation effected by the equipment. The reason for this is that mechanical fracture of many pieces of the feed occurs during the cleaning process; and in some processes crushers are deliberately incorporated in the flow to produce size degradation to free impurities from cleaned coal, thereby altering the washability characteristics of the material while in process. When such size degradation occurs in a cleaning process, it is quite possible that this crushing will result in a reduction in ash content in the finer sizes of cleaned coal when compared with the raw coal feed, even though no true separation has been effected. This is due to the fact that the finer sizes have been "sweetened" by the crushing of cleaned coal from some coarser size. Many formulas advocated in the past show high cleaning efficiencies

Jan 1, 1951

By Augustus Locke

San Francisco Meeting, October, 1911.) Two Opposed Interpretations of the Tonopah Structure.-The important geological publications concerning the Tonopah mining-district are those of Spurr 1 and of Burgess.2 In these publications are presented fundamental differences of interpretation, which are the more interesting because both authorities have had ample opportunity for observation, and because both are geologists of proved ability. I was vastly puzzled to know which had the better of it, and in order that I might reach a conclusion in my own mind, I recently spent some time in the district going over the physical evidence. Surprising as it may seem, this evidence looks agreeably conclusive. A review of it will, I believe, be of interest to those who are familiar with the previous publications. The general geological features of Tonopah are shown in Fig. 1, and the differences of interpretation referred to are outlined in the accompanying notes. Briefly, Burgess regards the various rocks as flows, lying in the order of their deposition. Spurr regards them in part as flows, and in part as flat-lying intrusives. The disagreement, then, concerns the rocks regarded on the one hand as intrusives, and, on the other hand, as flows. These rocks are chiefly the so-called calcitic andesite, the upper rhyolite, and the lower rhyolite. Economic Importance of the Question of Interpretation.-The economic importance of the question of interpretation is, of course, limited to its bearing on the probable distribution of 1 Geology of the Tonopah Mining District, Nevada, Professional Paper No. 42, U. S. Geological Survey (1905). Report on the Geology of the Property of the Montana-Tonopah Mining Co. (1910). An abstract of this report is given in the Mining and Scientific Press, vol. cii., No. 16,p. 560 (Apr. 22, 1911). 2 The Geology of the Producing Part of the Tonopah Mining District, Economic Geology, vol. iv., No. 8, pp. 681 to 712 (Dec., 1909).

Feb 1, 1912

By Harrison Everett Ashley

(Pittsburg Meeting, March, 1910.) Slimes are usually defined as all material passing a certain-sized sieve, which is invariably the finest sieve employed by each metallurgist in his tests; 100-mesh and 200-mesh have been taken as the limits by different writers in recent volumes of the Transactions ; 150-mesh is common practice. The reader of the first two volumes of Richards 1 is impressed by the inflexibility with which all grinding-arrangements are praised or condemned according as they make little or much slime. Until recently, one of the principal aims of the mill-man was to keep down the slimes. He was obliged to have separate apparatus for sand- and slime-treatment. The latter was sometimes puzzling and erratic. Often it was found most .economical to omit treatment of the slimes entirely, or to store them in immense basins or heaps, waiting for possible future improvements in methods of treatment. Recently, improved processes of agitation and filtration have made possible the successful extraction of values from many slimes. The tendency, when the metal is exceedingly finely disseminated, is to cut out all sand-treatment and to slime everything. These processes have been almost entirely mechanical in their conception, and it is the object of the present paper to show that certain chemical considerations may greatly hinder or assist their successful operation. It has long been a source of dissatisfaction to chemists that their analyses fail to be of much help to the clay-worker; that it is a matter of common occurrence for clays of closely identical ultimate chemical constitution to show the widest possible divergence in physical properties. * Published by permission of the Director of the U. S. Geological Survey. Ore Dressing (1903).

Aug 1, 1910

By A. Boltax

Precipitation processes occurring during both furnace cooling and aging of copper-iron albys were studied by means of electrical and magnetic measurements. On furnace cooling, two distinct stages in the precipitation process were detected; one occurring above and the other below 850° C. The kinetics of precipitation from quenched alloys were studied between 200° and 700°C. The reaction appears to be consistent with the concept of tmcleation of precipitate particles at dislocation loops formed by the clustering of quenched-in vacancies. A study Of in copper-iron alloys is particularly interesting because the combination of magnetic and electrical properties in these allovs provides a quantitative means of following the course of the precipitation reaction. (The details of precip-

Jan 1, 1961

By James W. Halley

"Fine-grained" steels have been standard products for many years. This paper describes an investigation of the effects of some of the more common grain-growth inhibitors used to produce these steels. The properties, response to heat-treatment, and the deoxidation practice necessary to produce "fine-grained" steels have been the subjects of numerous papers. It has been shown that a substantial quantity of aluminum is necessary to produce this type of steel, and it has been indicated that titanium and zirconium produce a similar result. For some time there was a lively argument between those who felt that aluminum refined the grain and those who felt that aluminum oxide was the effective agent. This argument subsided with an apparent victory for those promoting aluminum oxide. Most of the work on grain size has divided steels into two broad classifications based upon McQuaid and Ehn's original carburizing test at 1700°F or some similar test at this temperature. If the steel coarsened at this temperature, it was coarse grained, while if it did not it was he grained. Quantitative data concerning how much a certain amount of aluminum raised the coarsening temperature and affected the properties, all other factors being constant, are very meager. Similar information regarding titanium and zirconium is practically nonexistent. The published information on aluminum yields some quantitative information. Epstein, Nead and Washburn' gave the first quantitative information on the amount of aluminum necessary to prevent grain growth at 1700°F. They showed that the addition of a pound to a pound and a half of aluminum per ton (0.05 to 0.075 per cent) would assure steel that would not coarsen during a McQuaid-Ehn test at 1700°F. Herty, McBride and Houghg reported that a steel containing 0.020 per cent acid-soluble aluminum coarsened between 1742° and 1832°F., while steels containing 0.016 per cent and 0.017 per cent acid-soluble aluminum coarsened between 1652° and 1742°F. compared with similar aluminum-free steels that started to coarsen at 1580°F. Herty3 also showed a marked improvebent in low-temperature notched impact resistance with increasing acid-soluble aluminum up to 0.030 per cent. McQuaid4 compared the coarsening of steels containing 0.011 to 0.204 per cent total aluminum and found a maximum coarsening temperature at 0.098 per cent aluminum. He had no samples between 0.015 and 0.098 per cent aluminum. Houdrement6 found a marked decrease in coarsening temperature with aluminum contents above 0.50 per cent. Kinzel, Crafts and Egan6 found that aluminum and zirconium improved the low-temperature impact resistance of a low-alloy steel, while titanium was detrimental. Sims7 shows that sulphur increases the coarsening temperature and that the maximum coarsening temperature is between 0.04 and 0.06 per cent added aluminum. The fact that the coarsening temperature passes through a maximum with increasing aluminum content appears to be well established. The aluminum content that

Jan 1, 1947

By James W. Halley

"Fine-grained" steels have been standard products for many years. This paper describes an investigation of the effects of some of the more common grain-growth inhibitors used to produce these steels. The properties, response to heat-treatment, and the deoxidation practice necessary to produce "fine-grained" steels have been the subjects of numerous papers. It has been shown that a substantial quantity of aluminum is necessary to produce this type of steel, and it has been indicated that titanium and zirconium produce a similar result. For some time there was a lively argument between those who felt that aluminum refined the grain and those who felt that aluminum oxide was the effective agent. This argument subsided with an apparent victory for those promoting aluminum oxide. Most of the work on grain size has divided steels into two broad classifications based upon McQuaid and Ehn's original carburizing test at 1700°F or some similar test at this temperature. If the steel coarsened at this temperature, it was coarse grained, while if it did not it was he grained. Quantitative data concerning how much a certain amount of aluminum raised the coarsening temperature and affected the properties, all other factors being constant, are very meager. Similar information regarding titanium and zirconium is practically nonexistent. The published information on aluminum yields some quantitative information. Epstein, Nead and Washburn' gave the first quantitative information on the amount of aluminum necessary to prevent grain growth at 1700°F. They showed that the addition of a pound to a pound and a half of aluminum per ton (0.05 to 0.075 per cent) would assure steel that would not coarsen during a McQuaid-Ehn test at 1700°F. Herty, McBride and Houghg reported that a steel containing 0.020 per cent acid-soluble aluminum coarsened between 1742° and 1832°F., while steels containing 0.016 per cent and 0.017 per cent acid-soluble aluminum coarsened between 1652° and 1742°F. compared with similar aluminum-free steels that started to coarsen at 1580°F. Herty3 also showed a marked improvebent in low-temperature notched impact resistance with increasing acid-soluble aluminum up to 0.030 per cent. McQuaid4 compared the coarsening of steels containing 0.011 to 0.204 per cent total aluminum and found a maximum coarsening temperature at 0.098 per cent aluminum. He had no samples between 0.015 and 0.098 per cent aluminum. Houdrement6 found a marked decrease in coarsening temperature with aluminum contents above 0.50 per cent. Kinzel, Crafts and Egan6 found that aluminum and zirconium improved the low-temperature impact resistance of a low-alloy steel, while titanium was detrimental. Sims7 shows that sulphur increases the coarsening temperature and that the maximum coarsening temperature is between 0.04 and 0.06 per cent added aluminum. The fact that the coarsening temperature passes through a maximum with increasing aluminum content appears to be well established. The aluminum content that

Jan 1, 1947

By Y. L. Yao

The solubility limit of oxygeu in a titanionn at 850°C has been determined by magnetic measurements as 12.5 + 0.5 pct (29.0—30,9 at. pct). Also in the susceptibility-co~centmtion curve, there is n distinct but not sharp maximum at 19.0 * 0.5 z~t pet (40.5--42.1 at. pct), which indicates the presence of the 6 phase. The magnetic susceptibilities of the alloys of the titanium-oxygen system were determined byEhrlich in 1939.' is alloys were prepared by sintiring mixtures of titanium and its oxide at high temperatures. On the titanium-rich side, despite the fact that the alloy compositions he measured crossed two phase boundaries, the limited results obtained

Jan 1, 1960

By L. H. Robinson

Triaxial compression tests on Indiana limestone indicate that chemical additives in the pore fluids can increase or decrease the strength in plastic failure but not in brittle failure. Tests using a series of the sodium salts of dicarboxylic acids show that odd-number carbon-atom chains decrease the yield strength as much as 3.0 x 10 3 psi, and even-number carbon-atom chains increase the yield strength as much as 9.0 x 102 psi. ,The most effective chemical (sodium citrate) decreased the yield strength of Indiana limestone from 16.0 x 103 to 12.0 x 103 psi. The chemical additives investigated have no influence on microbit drilling rate when drilling with zero differential pressure. However, when drilling at a 2.0 x 103-psi pressure differeniial and using an odd-number carbon chain compound as the circulating fluid, the roller bit drilling rates were slower than with water whereas the drag bit drilling rates were faster. One even-number carbon chain compound added to the circulating fluid produces the opposite effect: the roller bit drilling rate is slightly faster than with water and the drag bit slower than with water. INTRODUCTION A Russian book by Rehbinderl published in 1944 generated much interest in the possibility of aiding and accelerating the destruction of solids by the action of a liquid in which the solids are deformed. This book describes a process in which microcracks are generated during elastic deformation. To describe this process, the rock is divided into three zones: (1) the zone in which the destruction takes place, (2) the predestruc-tion zone (an affected area immediately below the destroyed zone) and (3) the undisturbed specimen. Consider a load applied normally to a surface of an infinite slab of rock. Immediately below the point of application of the load, the rock is destroyed by compression or shear forces. Below this area of destruction, because of a great number of discontinuities ranging from defects to weak points in crystals of discontinuities in crystal latices, very small cracks are created in or between the crystals (often referred to as microcracks). Upon removing the load, the broken rock in the destroyed zone could be removed. In the lower predestruction zone, however, the microcracks in and between the crystals could disappear by the process of rehealing, i.e., the molecular attraction from one side of the crack to the other side being sufficient to completely eliminate the crack. Thus, a large number of these microcracks possibly exist only for a relatively short period of time. The concept of small cracks being generated within the crystals of a rock is not unreasonable. If the rock matrix is deformed below the yield point, some of the defects present within the crystalline structure could start small cracks through the interior of the grains. Upon removal of the load, these microcracks reheal (or the newly generated surfaces come back together) so that all evidence of cracks completely disappears. Under various types of loading, and in various types of fluids, the rehealing of these cracks would be time dependent. If a liquid adhered to the surface of a rock, it could penetrate into the microcracks and thus delay or prevent the rehealing process. This suggests that the prevention of healing of the microcracks may be dependent upon the wetting characteristics of the solid. Thus, rocks which are water-wet should be more easily destroyed in water than in nonpolar hydrocarbon liquid. Adsorption of a liquid could also reduce the free surface energy which could explain the decrease in strengths of materials under nonrepetitive-type loading. Rehbinder's work prompted Boozer, Hiller and Serdengecti 2 to examine the effects of pore fluids on the deformation of rocks subjected to triaxial compression over a range of confining pressures, temperatures and strain rates. Fluids which strongly adsorbed on the rock grain surfaces decreased the strength of sandstone and limestone, which deformed plastically. For certain strain

By Robert Lowrie

Nine intermetallic compounds were tested in tension at various temperatures. Seven exhibited extensive plastic deformation at elevated temperatures. Correlations of tensile strength and elongation are attempted with melting (decomposition) temperature, valence electron configurations of the component elements, heat of formation, crystal structure, density, and volume decrease accompanying compound formation. A LTHOUGH intermetallic compounds have been -tX known for many years, the study of their mechanical properties, particularly in tension, is just beginning. The problem has been unattractive because of the well-known, erratic behavior of brittle materials tested in tension. The strong influence of surface or internal flaws as stress raisers in non-ductile materials and the effect of eccentricity of loading in superimposing bending stresses on the state of tension in the specimen are extremely difficult to mitigate and impossible to completely eliminate. Thus, tensile properties determined for brittle materials, such as intermetallic compounds at temperatures low in comparison to their melting points, are at best only general guides to the values to be expected in an ideal test of a perfect specimen of the material. It is, nevertheless, surprising that apparently no attempt was made to follow up the pioneer work of Tammann and Dahl1 in this field. Working with crude apparatus, these investigators succeeded in showing unequivocally that at temperatures sufficiently close to their melting points (from 75" to 400°C for the compounds tested) intermetallic compounds did exhibit plasticity. This was indicated by the appearance of slip lines on the surface of the specimen. No observations of strength were made in these tests, which were of a compressive or indentation type. Rossi2 in 1932 attempted to study the physical and mechanical properties of single crystals of a group of intermetallic compounds. However, he was able to prepare only one material, Cu2Z8,, in the form of large, defect-free, single crystals. Thus, he was able to report only the relative fragility of the compounds at room temperature. He reported one compound, Ag,Zn,, to be somewhat plastic at room temperature and Cu,Si to be friable, the latter in agreement with results reported herein. Although test results are available only in classified literature, it has also been announced that MoSi, possesses some ductility at elevated temperatures." In 1948 and 1949 Savitskii and Savitskii and Baron -ublished their work on the hot extrusion of Mg-Zn, Al-Mg, and Cu-Zn compounds. Under the favorable state of stress existing for this process MgZn, MgZn,, MgZn,, ß (Al-Mg), ? (Al-Mg) and 0 (Cu-Zn) could be reduced by amounts up to 90 pct at elevated temperatures. These authors also report that hardnesses of Mg-Zn compounds decrease from room temperature values of about 300 kg per sq mm to 30 to 50 kg per sq mm at 325°C. They found that alloys consisting solely of one Mg-Zn compound were most resistant to softening on heating, mixtures of a compound and eutectic less resistant, and mixtures of two compounds least resistant. The more rapid softening of mixtures of

Jan 1, 1953

By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,' namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

By Jun Hino, P. G. Shewmon, P. A. Beck

THE investigations of Crussard,' of Guinier and Tennevin,' and of Dunn and Daniels," indicate that the subgrains formed in a cold worked and annealed metal are capable of growing at each other's expense during annealing, if the temperature of annealing is sufficiently high and the time is long enough. The results of Dunn and Daniels are particularly convincing in showing that subgrain growth is essentially the result of the free surface energy associated with the subboundaries. In subgrain growth, as in ordinary grain growth, energy is gained as a result of the decrease in total subboundary surface area per unit volume. Recently, Wood and Scrutton4 found that the rate of subgrain growth upon annealing increased very considerably, if simultaneously a creep strain was applied to the specimen at a low strain rate. Working with 99.98 pct pure fine-grained aluminum, these investigators found that the continuous X-ray diffraction back-reflection rings of material strained at room temperature remained continuous after heating for ten days at 250 °C. However, when heated at the same temperature under a stress of 1000 psi even for only three days, the formerly continuous X-ray diffraction rings broke up into numerous dots, which were fairly clearly separated from each other. The continuous X-ray diffraction rings were interpreted as indications of a very small subgrain size, not resolved by the X-ray diffraction method used. The breaking up of the continuous X-ray diffraction ring during annealing under stress was taken as an indication of a great increase in subgrain size, so that the individual subgrains could then be resolved. The effect of simultaneous strain at a low strain rate in accelerating subgrain growth, discovered by Wood and Scrutton and designated by them as "cell growth," is of fundamental importance. The experiments described in this note were carried out in order to confirm Wood and Scrutton's results by direct metallographic observation. Also, information was sought as to the minimum creep strain necessary to produce this effect. A fine grained high purity aluminum strip was prepared by alternate 33 pct rolling and annealing treatments for 1 hr at 350°C. Specimens cut from this strip were subjected to a relatively fast creep strain of 7.2 pct in 3.5 min at 300°C under a constant load initially corresponding to 1185 psi. The subgrains set up were large enough (about 0.015 to 0.03 mm) to be clearly observed (Fig. 1) at X200 magnification with polarized light, after electrolytic polishing and anodic etching, producing a fine oxide film." The corresponding X-ray diffraction pattern is shown in Fig. la. After the fast creep strain treatment a portion of the specimen was subjected to a creep strain of 8.3 pct in 44 hr at 350°C under a constant load initially corresponding to 320 psi. Another portion, annealed under the same conditions, but not strained, served as control specimen. The subgrain size of a typical area of the specimen annealed under strain and of the one annealed without strain is shown in Figs. 2 and 3 (X-ray diffraction patterns, Figs. 2a and 3a). Annealing without strain produced clearly observable subgrain growth (subgrain size: about 0.03 to 0.05 mm). The effect of simultaneous strain was to increase greatly the rate of subgrain growth (resulting in a subgrain size of approximately 0.05 to 0.13 mm), in accordance with Wood and Scrutton. In another experiment, the effect of the amount of simultaneous strain was studied. The initial subgrain structure was set up by fast creep, as described previously. The specimen was then heated at 350 °C under a constant load initially corresponding to 320 psi, as above, for 2.2 hr (0.24 pct strain), and 8.8 hr (0.58 pct strain). Comparison with the corresponding unstrained control specimens by means of X-ray diffraction showed that 0.58 pct strain definitely had an effect, but the effect of 0.24 pct strain was doubtful.

Jan 1, 1953

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By C. S. Barrett, C. T. Haller

Twinning in magnesium is known to occur profusely under certain conditions, and when it occurs in polycrystalline materials it brings about a partial or even a complete change in the preferred orientation. The amount of research on this subject, however, has not been in proportion to its importance as a mechanism of deformation and reorientation. Much of the research has been limited to twinning in single crystals. The present study1 concerns polycrystalline sheet, and is an investigation of the twinning produced by plastic deformation as a function of the following variables: 1. Direction and type of deformation. 2. Amount of deformation. 3. Speed of deformation. 4. Temperature of deformation 5. Composition and temper of the sheet. 6. Twins previously produced. 7. Twins previously produced, then annealed. By proper control of these variables it is shown that, on a laboratory scale, samples can be produced that are free from preferred orientations. The materials used were samples of commercial magnesium-alloy sheets with nominal compositions given in Table I. X-ray diffraction was used in most of this work to detect the twins and to estimate the amount of twinning. Since twinning on (102) planes causes a re-orientation of the crystal lattice by 86", it is very easy to study with X-ray diffraction patterns, particularly if one notices the diffraction ring from the basal plane— the 002 reflection. By properly directing the X-ray beam, it is possible to produce 002 reflections from twinned material at, say, the 6 and 12 o'clock positions on the 002 ring, with the untwinned material reflecting to 3 and 9 o'clock positions; and by judging the relative intensity of the arcs on the diffraction ring at these positions, it is possible to judge the amount of twinned material relative to the untwinned. This X-ray method of estimating the amount of twinning is generally superior to metallo-graphic observation, for it was found

Jan 1, 1947

By D. Weinstein

The high temperature mechanical properties of stainless steels after fast neutron irradiation are discussed in the light of effects caused by lattice dattmage and effects caused by helium generated from n,a transmutations. Embrittlement at high temperatures is due to helium accumulation at grain boundaries and to cavity formation and proPagation along grain boundaries. Following from the embrittlement mechanism, it is suggested that when deformation occurs by mechanisms associated with super plasticity, helium ac-curnulation at boundaries should be attenuated and cavities, if formed, should be nonpropagating. As the mean free Path between interphase boundaries of a two-phase Fe-Cr-Ni alloy was decreased, the degree of superplastic deforrnation at 870°C increased, as vneaszired by total elongation and by the expottent m = a log 'a/a log 'i. This alloy and type 304 stainless steel were cyclotron irradiated in an a-particle beam to a helium concentration of -1 x 10 atom He per atom. The stainless steel specimen was embrittled, but the ductility of irradiated two-phase Fe-Cr-Ni alloys correlated with the values of. m during 'defor-malion. The .finest grained, helium-injected specimens that deforrned with highest m values exhibited the largest elongations to ,fracture. These results could be correlated with metallographic observations of cavity behavior: the propensity for intergranular propagation was lessened as the m value increased. It is concluded that superplastic deformation is ef-fectizle in attenuating helium embrittlement at elevated temperatures. One of the principal problems associated with development of fast breeder reactors is application of alloys such that suitable fuel cladding results. Stainless steels and other Fe-Cr-Ni alloys, because of highly acceptable nuclear characteristics, represent the primary materials for this component, and an exhaustive research and development effort is being conducted. The main deficiency of these materials has been a severe loss of ductility at high temperatures after fast neutron irradiation. An extensive body of mechanical property data and microstructural observations has provided an adequate phenomenological description of embrittlement; in conjunction with transmission electron microscopy studies, a reasonably acceptable embrittlement mechanism has been obtained. Following from this mechanism, it is suggested in the present work that ductility would be enhanced if deformation could occur by mechanisms associated with the phenomenon of superplasticity. Experiments to test this hypothesis have been conducted, and the results are presented and discussed in this paper. IRRADIATION EMBRITTLEMENT AT HIGH TEMPERATURE Austenitic stainless steels have been irradiated to accumulated fast neutron fluences of 1020 to 1022 nvt at temperatures between 60" and 600°C. Specimens that have been exposed to these conditions and subsequently tensile tested at temperatures between 600" and about 900°C exhibit approximately 5 pct total elongation to fracture.'-3 For unirradiated specimens receiving a nearly identical thermal exposure, total elongation at these test temperatures is about 45 pct. Examination of irradiated specimens has shown that fracture propagation is entirely intergranular. These phenomenological aspects of irradiation embrittle-ment at elevated temperatures are well known and are not generally disputed. Although the explanation of this phenomenon has been controversial, a mechanism for ernbrittlement has emerged that accounts reasonably well for the observed mechanical behavior. The controversy resulted primarily from an indeterminate role of neutron-in-duced lattice damage, if any, and a presumed, but experimentally unverified, contribution to embrittle-ment from helium generated by n,a transmutations. Recently, Holmes and coworkers4 have conducted experiments that separate these effects, and the results are instructive in formulation of the ernbrittlement mechanism. Holmes el al.4 irradiated type 304 stainless steel in EBR-I1 to a fluence of 1.4 x 1022 nvt (E > 0.18 mev); the irradiation temperature was 538" * 48°C or, in terms of absolute melting point, 0.49 * 0.03 T,. After irradiation, tensile tests were conducted at temperatures of 21" to 870.C, the specimens first being annealed for 30 min at each test temperature. In addition, thin sections of irradiated specimens were annealed for 1 hr at identical temperatures, electro and examined by transmission electron microscopy. Thus, for a given temperature, it was possible to correlate mechanical properties with the defect structure. At room temperature, the yield stress of irradiated specimens was a factor of 2.5 higher than unirradi-ated specimens exposed to an equivalent thermal history. Electron microscopic examination of the irradiated specimen revealed a high density of lattice damage in the form of Frank sessile dislocation loops and polyhedral voids. Holmes et al.4 concluded that the presence of this defect substructure caused the increase in yield stress and that after irradiation in a fast neutron flux at 0.49 Tm, substantial lattice dam-age persists. Annealing at progressively higher tem-

Jan 1, 1970

By John Mark Patek

Knowledge of the relative floatability of silicate minerals is increasing in importance as flotation is being applied to the concentration of nonsulfides. Many silicates are in themselves commercial products amenable to concentration by flotation. Moreover, the selective flotation of other nonsulfide minerals, such as cassiterite, depends largely upon the floatability of associated gangue silicates. Differences in floatability existing between the various silicates have not- been sufficiently appreciated; for example, the feldspars that differ greatly in floatability have generally been merely treated as "feldspar." It was the purpose of the work described in this paper to determine by experiment the differences in floatability between silicates; to investigate the causes for such differences, and to discover a means of predetermining approximate floatability without the necessity of experimentation. Determining Floatability The relative floatability of 20 silicates so selected as to represent all of the more common silicate types1 was obtained by flotation tests enumerated in Table 1. The mineral to be floated was crushed dry on a steel plate, and screened repeatedly during crushing through an 80-mesh screen in order to produce a sand with all grains as close to 80 mesh as possible. The sand was placed in dilute (6N) hydrochloric acid until free of soluble foreign material, and then washed with tap water about ten times in order to remove both acid and fines. The resultant product, which averaged 82 per cent plus 200 mesh, was floated in 50-gram charges in a 50-gram Denver celluloid flotation machine with 0.008 gram of terpineol, and from 0.01 to 0.05 gram of oleic acid in a solution acidified with sulfuric acid. The degree of separation of one mineral from another was determined by counting under a nlicroscope the grains of each mineral, both in the concentrate and in the tailings, and comparing their relative abundance in each. Unless the comparison showed a decided difference in amount,

Jan 1, 1935