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By Walter Harvey Weed

The enrichment of mineral-veins as a result of the migration of material from an upper oxidized or disintegrated part of a vein to a lower level, where it is redeposited, is now, I believe, quite generally accepted as one explanation of the occurrence of bonanzas in gold- and silver-veins, as well as that of bodies of high-grade ores in cupriferous deposits.* Vogt has called attention† to the fact that there are numerous examples of such rich shoots which are " of exclusively primary character, and dependent upon the laws which governed the original ore-deposition." To this I would add that there are also other examples which are neither of primary origin nor due to descending waters, but. result from a reopening of the veins and their penetration by ascending heated waters whose metallic contents are deposited by reaction with the primary pyrite (and possibly other minerals), forming "secondary" enrichments. My studies of the copper-veins of Butte, Montana, show: That the veins there are of several ages and systems; that the older primary quartz-pyrite veins were reopened by later movements, correlated with a period of volcanic activity; and that they were penetrated by hot alkaline waters carrying copper and arsenic in solution, which was deposited presumably by reaction with the pyrite of the original vein. The enormous development of the Butte deposits, attendant upon the extraction of nearly 10,000 tons of ore a day, has revealed many facts concerning the nature and distribution of the ores. Enargite, the copper sulpharsenate, formerly a relatively rare mineral, is now found to be the chief ore of some veins,

Jan 1, 1903

By R. J. Colony

The failure, or disintegration, of concrete in structures, even when the cement, sand, and coarse aggregate used have passed satisfactorily all tests and inspections, is not uncommon. Such failures occur even when proper methods of mixing and placing have been used and where weather conditions were correct. In these cases, the origin of the trouble must be sought in the cement; therefore some additional mode of determining the quality of cement must be employed. The problem is to find a simple, usable, easily applied method that will supplement the standard tests. The solution of this problem involves a knowledge of the chemical composition of Portland cements, also of their constitution (or componental composition), as the behavior of a cement, when gaged, is dependent on the physical and chemical characters of the compounds of which it is composed, the proportions existing between them, and the fineness of grinding. It is likewise essential to know the character, behavior, and composition of the hydration products of Portland cement. The most promising method of attack makes use of chemical, mechanical, and petrographic methods. Chemical, by determining quantitatively not only the usual constituents, but the carbon dioxide and water. Mechanical, by determining the fineness with the air analyzer,' which separates into fractions of various grain dimensions all of that portion which in the ordinary sieve test passes the 200-mesh sieve and constitutes at least 75 per cent. of the total cement. These fractions may be further studied chemically and petrographically and micrometric measurements can be made of the grains. Petrographic, by the method of immersion, and by making thin sections from test pats of both neat cements and standard mortars. Normal Portland cement is composed of mechanical mixtures of definite chemical compounds having constant chemical and physical properties. In the order of their cementing qualities these are: Tri-

Jan 1, 1922

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By I. N. Knapp

I Herewith present some notes on the use of Portland cement to cement in the casing, and for plugging, to exclude water from oil and gas wells, and the methods employed. I have used my best efforts to. make each step of the operation of cementing wells perfectly clear. The information is the result of actual experience and observation. The illustrations are from original drawings made especially for this paper. Portland Cement It is not necessary to discuss here the manufacture of cement. Any established brand of the slower setting Portland cements may be purchased with the confidence that it will harden, if properly used, and exclude water from and plug wells efficiently. Setting.—By the setting of cement is meant its initial change from a soft or plastic mortar to a friable solid. After the cement has become thoroughly set it is still very weak and can be readily pulverized in the fingers. Setting is thought to be effected by the crystallizing out of the silicate and the aluminate of lime, which are soluble in water in their anhydrous form. After dissolving in the water they pass to the hydrated state, in which they are insoluble, and hence are precipitated in a crystalline form. Ordinarily neat Portland cement mortar remains perfectly plastic for from 1 to 1 1/2 hr. after mixing with water at about 70" F. A higher temperature accelerates and a lower retards setting.. Hardening.—This is due to a continual crystallization of salts from solution, and to further chemical and physical changes which develop slowly, but which continue for long periods of time. Testing.—It is no more necessary for an operator to go into the scientific testing of cement to be used in a well than to so test the pipe used. He must depend for the quality of each on the tests and reliability of the manufacturer. Cement or pipe may be damaged in shipment so

Jan 1, 1915

By W. D. Robertson

The effect of a tensile stress in accelerating the corrosion-cracking of certain alloys of aluminum, magnesium and iron is widely recognized. The literature is extensive and it is only necessary to cite the recent ASTM—AIME Symposium,l There are, however, no experimental data conclusively showing the effect of an applied compres-sive stress. It has been inferred, from the generally accepted mechanism postulated for the acceleration of corrosion by an applied tensile stress, that a compressive stress would inhibit corrosion. Furthermore, it is observed that corrosion cracks invariably start on the tension side of a specimen bent as a simple beam. This observation has led to the suggestion that shot-peening of the surface would inhibit or eliminate stress-corrosion cracking in magnesium alloys and aluminum alloys. However, the degree of inhibition produced by shot-peening does not appear in the literature except for the above qualitative references which are unsupported by experimental data. Moreover, while peening undoubtedly imposes a surface compressive stress, the alteration of the surface by the severe cold-working involved complicates the interpretation of the results with respect to the effect of a compressive stress alone. If corrosion proceeds along preferential paths produced by precipitation from solid solution, it is easily understood how a component of tensile stress normal to these paths will accelerate the corrosion and lead to ultimate failure. On the other hand, if the metallurgical conditions are such as to create preferential corrosion paths, then it is difficult to understand how a compressive Stress, produced by shot-~eening Or any other method, can inhibit corrosion except in the sense that the accelerating factor is removed. Thus, if the basic corrosion mechanism remains unaltered, there should be little or no inhibition resulting from the application of a compressive stress if inhibition is defined as the reduction of the degree of corrosion below that experienced in the unstressed state. The experiment described below was performed to isolate and evaluate the effect of a compressive stress on the corrosion and stress-corrosion cracking of a high strength aluminum alloy (24-S); and, by a Comparison of the corrosion rate of 'pecimens subjected to an applied tensile stress, compressive stress and in the unstressed state, to clarify the role of stress in intergranular corrosion. Experimental Procedure The experiment was conducted with the aluminum-copper-magnesium alloy known as Duralumin 24-S.* Specimens, 0.064-in. thick, in the form of I-in. wide strips sheared parallel to the rolling direction,

Jan 1, 1949

By H. A. Schwartz

THE spheroidal form of the temper carbon nodules in malleable cast iron and of the graphite mottles of "mottled" cast iron suggests that in both all the graphite in a given mottle or nodule grew from a single center of crystallization or nucleus. ? There is, however, a distinct metallo-graphic difference between the mottle and the nodule; the area of mother metal impoverished in combined carbon by the crystallization of graphite in a mottle is practically coextensive with the ramifications of the graphite, while the impoverished zone of metal corresponding to a given nodule is always larger, and usually much larger, than the approximately spherical mass of graphite crystals forming the nodules. Furthermore, the mottle probably is formed during freezing and the nodule almost always at a considerably lower temperature. Assuming that the nodules or mottles can be used as a measure of the existing nuclei (capable of germination) we propose to record certain observations as to the graphitizing reaction in the light of the number and habits of growth of these nuclei. The present authors, in cooperation with others1-7, have reported upon various cognate aspects of the problem. The fact that temper carbon is a mass of flakes and not a solid granule has become well recog-nized since the introduction of an improved polishing technique8,9,10 for cast iron. The problem of deriving from the circular planar intercepts

Jan 1, 1936

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The Blast Furnace Studies Section, Metallurgieal Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1940

By Robert J. Anderson

DURing the past 5 years no subject has aroused more interest or received more attention among mill operators than flotation. One reason for this is, undoubtedly, the remarkable success of the process in Australia where that country has risen to the position of furnishing one-fifth of the world's supply of zinc. The plant of the Butte & Superior Copper Co., designed by James M. Hyde in 1912, was the first important large flotation plant in this country; other installations have been made since then with considerable frequency, particularly so in the last 2 years. Without going into complete detail, it may be safely said that although flotation is a highly successful commercial process, it is more or less on an empirical basis. Upon scanning the literature, it is found that the flotation investigations have, in the main, dealt with a solution of the problems which accrue to practise; until recently no attempt was made to remove the difficulties in the way of the formulation of a consistent and harmonious theory. Of late this phase of the work has been receiving considerable attention, particularly by the United States Bureau of Mines at its Salt Lake City station, by the Mellon Institute at Pittsburgh, by the General Engineering Co. at Salt Lake City, by many of the mining schools, and private individuals almost ad infinitum. There is, at present, an enormous amount of laboratory work being carried on in flotation research, and probably the time is not far away when a generally acceptable explanation of flotation phenomena can be set forth. However, at this time, it seems as though the current technology is befogged with a superabundance of contradictory evidence; this confusion can only be dispelled as time proceeds and the knowledge of the subject becomes more complete. Many phenomena are supposed to contribute to the flotation of minerals, whether in whole or in part is a mooted question. I shall only sketch roughly the present tendency of ideas and make no reference to the first early and crude notions which have little value other than histori-

Jan 1, 1917

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The Blast Furnace Studies Section, Metallurgieal Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1940

By R. G. Agarwal, Ramey Jr. H. J., Al-Hussainy R.

Although it has long been realized that gas recovery from a water-drive gas reservoir may be poor because of high residual saturations under water drive, it appears that only limited infomlation on the subject has been available until recently. This study was performed to show the qiiantitative potential importance of water influx. Results indicate that gas recovery may be very low in some cases: perhaps as low as 45 per cent of the initial gas in place. Gas recovery under water drive appear to depend in an important was on: (I) the prodirction rate and manner of production; (2) the residual gas saturation; (3) aquifer propertie.); and (4) the volumetric displacement effciency of water invading the gas reservoir. The manner of estimating water-drive gas reservoir recovery can vary considerably. Examples are: the steady-state tnethorl. the Hurst modified steady-state method, and various unsteady-state methods such ac. those of van Ever-dingen-Hurst, Hurst, and Carter-Tracy. The Carter-Tracy water influx expression was used in this study. In certain cases, it appears that gas recovery can be increased significantly by controlling the production rate and manner of production. For this reason, the potential importance of water influx in particular gas reservoirs should he investigated early to permit adequtrtr planning lo optirtize the pay reserves. INTRODUCTION In recent years, the economic importance of natural gas production has become increasingly apparent. This has been evidenced by more intensive exploration efforts aimed at gas production, and exploitation of both deep, as well as low-permeability gas reservoirs. Technical developments such as deep-penetration fracturing have made development of such formations economically feasible. Unfortunately, water influx has forced abandonment of a number of gas reservoirs at extraordinarily high pressures. Although reservoir engineering methods for estimating water influx have long been available, it appears that application of these methods to the water-drive gas reservoir has been sporadic.'a Available methods for estimating water influx which can be applied to the water-drive gas reservoir problem include the steady-state method,1 the Hurst modified steady-state method and various unsteady-state methods such as those of van Everdingen-Hurst. Hurst, and Carter-Tracy. Interesting applications of these solu- tions to gas reservoir and the aquifer gas-storage problems have appeared recently.3,12,14 The experimental study of residual gas saturations under water drive by Geffen et al. in 1952 indicated that residual gas saturations could be extremely high. A value of 35 per cent of pore volume is often used in field practice when specific information is not available. The study of Geffen et al. showed that residual gas saturation might be much higher in some cases. Naar and Henderson concluded that the residual non-wetting phase saturation under imbibition should be about half of the initial non-wetting phase saturation. The Naar and Henderson result that residual gas saturation under water influx should be about half the original gas saturation is recommended as an estimate if laboratory measurements are not available. Thus, it is clear that a considerable portion of the initial gas in place might be trapped in a water-drive gas reservoir as residual gas at high pressure. A full water-drive would result in loss of residual gas trapped at initial reser.voir pressure. Consideration of transient aquifer behavior leads to the conclusion that high-rate production of water-drive gas reservoirs could result in improved gas recovery by reduction of the abandonment pressure. However, there appears to be little quantitative information on this possibility. One of the few advantages of water-drive gas production appears to be improved deliverability through water-drive support of the reservoir pressure. There may also be an advantage in higher condensate recovery caused by pressure maintenance for gas-condensate water-drive reservoirs. In view of the preceding, this study was made to assess the potential importance of water-drive in gas reservoir engineering. The Carter-Tracy approximate water-influx expression was used because this equation offers some advantages in hand-calculation which do not appear to have been generally recognized.' However, calculations were performed in the main with a high-speed digital computer to permit evaluation of the effect of water-drive under a large variety of conditions. CALCULATION METHOD Water-drive gas reservoir performance can be estimated in a manner completely analogous to oil reservoir calculations: a materials balance is written for the reservoir, and a water influx equation is written for the aquifer. Siniltaneous solution provides the cun~ulative water influx and the reservoir pressure. When reservoir performance data (gas produced and reservoir pressures) are available, it is usually possible to match performance data to determine the initial gas in place and the water influx parameters —

Jan 1, 1966

By Robert Mehl

PART I. ORIENTATION RELATIONSHIPS IN OXIDE LAYERS Oriented overgrowths and intergrowths among both metallic and nonmetallic substances have been recognized and studied for well over a century. The work of Widmanstätten in 1808 on the geometrical struc-ture in meteorites, a structure known by his name, demonstrated that oriented intergrowths can occur in purely metallic systems. This fact led to much of the early microscopic study of alloys, contributing greatly to the advance of physical metallurgy. The problem has been attacked again in recent years in a comprehensive fashion, with the object of dis-covering what atomic movements may occur during phase changes in alloy systems. Much of this work has appeared in the A.I.M.E. TRANS-ACTIONS in a series of papers published by Mehl and coworkers beginning in 19311. Although many aspects of this general problem remain unsolved, it may be said that the orientation of a new phase forming by precipitation from solid solution or by transformation invariably bears, a unique relationship to the orientation of the phase from which it formed, and that similarity in atomic patterns on atomic planes in the two phases play an important part in determining the orientation relationship. Analogous orientation relationships exist in oriented intergrowths in nonmetallic systems-mineral or inorganic. In 1827 Haidinger2 dis-covered natural intergrowths of hematite and magnetite, and demon-strated that the rough form of the magnetite octahedrons was delineated by small crystals of hematite, of which the basal (00.1) planes lay parallel to the octahedral cleavage planes of the magnetite. The description of this orientation relationship was later completed by von Rath3, who showed that the edge (00-1):(10-1) in hematite lies normal to the [111]

Jan 1, 1937

By John J. Secretary Egan

The present list of problems relating to the physical chemistry of steelmaking has been prepared by the Committee on the Physical Chemistry of Steelmaking, from answers to a questionnaire submitted to a number of metallurgists engaged in both industrial and educational work throughout the United States. The purpose of the project is to make available to research laboratories a list of problems, all reduced to their simplest terms, the solution of which would aid in creating a better understanding of the steelmaking process. It is not intended to restrict the problems to practical steelmaking. The list also includes the study of the properties, and their correlation, as well as the physical and chemical reactions, of all substances that occur or that may be in any way associated with steelmaking operations, such as metallic substances, refractories, nonmetallic inclusions, and the constituents of slags. Many of the problems can be carried out in university or other research laboratories. Others may be most successfully attacked by cooperation of the research men with the operating personnel. It is the Committee's earnest wish that this cooperation be fostered. It is requested that investigators who are working on any of the problems listed and who anticipate future publication of their results, notify the Secretary of the Committee that such investigation is in progress. Suggested additions to the present list are also requested. The Committee is undertaking to act as a clearing house for information regarding the topics in this field that are being actually studied. Interested persons are invited to correspond with the Secretary. I. Data involved in the state of equilibrium for the various systems (laboratory work, almost entirely). A. Specific heats, heats of formation, entropies and free energies of various PURE ELEMENTS OR COMPOUNDS; ALSO CERTAIN TYPICAL SLAGS AND REFRACTORIES I. Determination of specific heats and entropies of oxides, sulphides, nitrides, etc, over a wide temperature range. 2. Determination of free energies of oxides, sulphides, nitrides, etc., over a wide temperature range. 3. Determination of the heats of formation of the oxides, sulphides, nitrides, etc. 4. Determination of the thermodynamic properties of the more important mineral-ogical constituents of the basic open-hearth slags such as calcium silicates, calcium phosphates, calcium ferrites, manganese silicates, FeO and Fe2O3. 5. Determination of the specific heats of open-hearth slags, including liquid silicates, if possible.

Jan 1, 1941

By John J. Secretary Egan

The present list of problems relating to the physical chemistry of steelmaking has been prepared by the Committee on the Physical Chemistry of Steelmaking, from answers to a questionnaire submitted to a number of metallurgists engaged in both industrial and educational work throughout the United States. The purpose of the project is to make available to research laboratories a list of problems, all reduced to their simplest terms, the solution of which would aid in creating a better understanding of the steelmaking process. It is not intended to restrict the problems to practical steelmaking. The list also includes the study of the properties, and their correlation, as well as the physical and chemical reactions, of all substances that occur or that may be in any way associated with steelmaking operations, such as metallic substances, refractories, nonmetallic inclusions, and the constituents of slags. Many of the problems can be carried out in university or other research laboratories. Others may be most successfully attacked by cooperation of the research men with the operating personnel. It is the Committee's earnest wish that this cooperation be fostered. It is requested that investigators who are working on any of the problems listed and who anticipate future publication of their results, notify the Secretary of the Committee that such investigation is in progress. Suggested additions to the present list are also requested. The Committee is undertaking to act as a clearing house for information regarding the topics in this field that are being actually studied. Interested persons are invited to correspond with the Secretary. I. Data involved in the state of equilibrium for the various systems (laboratory work, almost entirely). A. Specific heats, heats of formation, entropies and free energies of various PURE ELEMENTS OR COMPOUNDS; ALSO CERTAIN TYPICAL SLAGS AND REFRACTORIES I. Determination of specific heats and entropies of oxides, sulphides, nitrides, etc, over a wide temperature range. 2. Determination of free energies of oxides, sulphides, nitrides, etc., over a wide temperature range. 3. Determination of the heats of formation of the oxides, sulphides, nitrides, etc. 4. Determination of the thermodynamic properties of the more important mineral-ogical constituents of the basic open-hearth slags such as calcium silicates, calcium phosphates, calcium ferrites, manganese silicates, FeO and Fe2O3. 5. Determination of the specific heats of open-hearth slags, including liquid silicates, if possible.

Jan 1, 1941

By D. Weinstein, F. C. Holtz

AS a possible method of improving the elevated temperature strength properties of zirconium, an investigation was initiated on the feasibility of producing a dispersion-strengthened material. Because of the high reactivity of zirconium, its high solubility for oxygen, and the stability of the Zr-0 solid solution, the major problem in such a development is choice of a suitable dispersant. Thus, in the present investigation we were concerned primarily with the stability of various dispersants in the zirconium matrix. The experimental procedure consisted of blending powders of zirconium and a dispersant, followed by cold compaction and extrusion. The best available source of -325 mesh zirconium powder contained between 1500 and 3500 ppm Oz; to this material, powders of zirconium carbide (5 p max), vanadium carbide (5 p max), alumina (0.03 p average), lan-thana (0.8 to 2 p), ceria (0.8 to 2 p), yttria (0.8 to 2 p), calcia (44 p rnax), or thoria (0.6 to 0.8 p) were added in amounts of 7 vol pct and compacted at 65 tsi. A cylindrical compact having a density between 70 and 80 pct of theoretical and dimensions of 1 in. diam by 1-114 in. high was thus produced. After canning in copper, these billets could be extruded (5: 1) on a 54-ton capacity, slow-traverse hydraulic press with the billet temperature at 1550°F and the extrusion die at 900°F. However, lack of densifica-tion of some of the extruded billets necessitated ratios of at least 23 :1. Ultimately, all billets were successfully extruded at 1500°F to 0.190 in. diam (32 :I), fully dense rods using a 200-ton capacity press and a ram speed of 90 ipm. The microstructures of as-extruded Zr-7 vol pct LazOS and Zr-7 vol pct Y2Os are shown in Fig. l(a) and (c), respectively. These structures are similar to all the as-extruded materials and consist of an elongated, single-phase zirconium matrix dispersed with oxide or carbide particles. Very little porosity is observed, and the interface between matrix and particles appears satisfactory. The size and distribution of particles, however, are not ideally of the type desired for dispersion strengthening. Since the primary study was of particle stability with respect to zirconium, no attempt was made to overcome agglomeration during powder blending and fabrication. Some areas exhibit fine, well-distributed particles; undoubtedly, a small proportion is submicroscopic and has the

Jan 1, 1963

By R. C. Canby

The difficulty of exact neutralization by ammonia of the acid solution obtained in the determination of arsenic by the method of fusion with carbonate of soda and nitrate of potassium, led me to try the effect of neutralization by oxide of zinc. I obtained most satisfactory results, and found a great saving of time. The oxide of zinc being added in excess, there is no delicate testing with lit? mils paper and tedious alternate adding of dilute ammonia arid acid until the proper point is reached. The excess of oxide of zinc, too, seems to hold, from the filter, the gelatinous silica and alumina, which are usually precipitated upon neutralization, and thus to render the washing of the precipitated arseniate of silver almost invariably much more rapid. Except the substitution of the neutralization by oxide of zinc for the more tedious method by ammonia, the details of the process are practically the same as those published by Mr. Richard Pearce, of Argo, Colorado (Proceedings of the Colorado Scientific Society, vol. i.), who shows what very accurate results can be obtained by the fusion process. I have made numerous tests of comparison between the two methods of neutralization, and find that those by the oxide of zinc agree almost exactly with the old method. Increasing the quantity of nitric acid, even to considerable excess, to be neutralized by the oxide of zinc did not affect the precipitation of arseniate of silver. The process may be outlined as follows : Take 4 to 1 gramme finely pulverized ore, and mix in a porcelain crucible with eight to ten times its weight of a mixture of equal parts of carbonate of soda and nitrate of potassium (Kerl. Metallurgische Probirkunst gives 4 to 5 nitre to 14 soda). Gradually bring to fusion and keep so, three to five minutes. Cool. Disintegrate in hot water. Filter and wash with hot water. Acidify the filtrate with nitric acid, and boil to expel carbonic acid and nitrous fumes. Cool. Add an excess of an emulsion of oxide of zinc. The bottom of the beaker should have quite a layer of oxide of zinc, after stirring.

Jan 1, 1889

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors1 determined the constitution of copper-silicon-manganese alloys contailling over go per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper.2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 2o c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. 'I'able I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. X few other changes will be noted (No. 138 at 450°C., No. 147 at 550°C., Nos. 153 and 149 at 75o°C.). The change from liquid to beta in equilibrium with kappa in No. 137 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. I to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the K-a + Y change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300' and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 + 0.03 per cent or 2.42 ±. 0.05 per cent were cast in ingots of 3-in: diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 700°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By Walter R. Hibbard, Cyril Stanley Smith

IN 1929 one of the authors' determined the constitution of copper-silicon-manganese alloys containing over 90 per cent copper. Through a combination of circumstances the presence of the copper-silicon kappa phase was overlooked in both binary and ternary systems. In the binary system the omission has already been rectified.2,3 To establish the limits of this phase in the ternary system, the samples that had been heat-treated at the time of the original research have now been re-examined, using more careful technique. Full details of the compositions used and the temperatures and times of heat-treatment are to be found in the earlier paper .2 The etching reagent now used to distinguish the kappa phase had the following composition: hydrogen peroxide (30 vol.), 20 c.c.; water, 25 c.c.; 20 per cent potassium hydroxide solution, 5 c.c.; ammonium hydroxide (0.90 sp. gr.), 50 c.c. Table I lists the newly observed structures. In virtually every case the constituents are the same as those previously recorded, except where kappa is now shown to be present as a result of the improved etching technique. A few other changes will be noted (No. 138 at 450°C., No. 149 at 550°C., Nos. 153 and 149 at 750°C.). The change from liquid to beta in equilibrium with kappa in No. 139 at 800°C. is based upon newly heat-treated samples. The alloy is very near the solidus at 800°C. and probably there was a slight error in the old heat-treatment temperature. The isothermal phase diagrams shown in Figs. 1 to 6 were reconstructed on the basis of the new studies. The presence of manganese does not greatly change the composition limits of the kappa phase or cause the [K = a + ?] change to occur at a markedly different temperature. There is some uncertainty regarding the range of existence of beta, for alloys were not spaced very closely in composition. The proposed diagrams, however, are in accordance with the available experimental data and with the dictates of the phase rule. Theoretically necessary fields with no experimental points are delineated by dotted lines. The alpha boundaries at all temperatures are shown together in Fig. 7. This includes also some additional points on the alpha boundary at 300° and 350°C., which were obtained as a result of electrical-conductivity measurements. Two series of seven alloys with increasing manganese content but with silicon constant at 1.90 ± 0.03 per cent or 2.42 ± 0.05 per cent were cast in ingots of 3-in, diameter. These were hot-rolled, homogenized and drawn to wire, finished at 0.08-in. diameter with a 61 per cent reduction of area following annealing at 900°C. Conductivity determinations were made before and after annealing for 30 days at 300°C. or 21 days at 350°C. Figs. 8 and 9 show the change of conductivity produced by this annealing, plotted against manganese

Jan 1, 1942

By J. H. Wernick, S. Geller

A number of new AB, compounds, in which A is a rare earth or yttrium atom and B is Al, Mn, Fe, Co, or Ni, having the cubic MgCu, structure (Laves phase) are reported. In most of the compounds, the interatomic distances are normal; the lanthanide contraction is observed. However, in the compounds CeB2, B = Fe, Co, Ni, Ce appears to have a valence substantially greater than three; in CeAl2, Ce appears to be trivalent. These results are interpreted as vesulting from an energetically more favorable situation for the 4f electron of Ce to be lost to the 3d band of Fe, Co, nnd Ni. Evidence for the existence of homogeneitj! ranges in these compounds is presented. THE purpose of this paper is to report on the crys-tallographic investigations of a large number of new compounds, Table I, with the MgCuz structure (cubic Laves phase). It is a part of a continuing study of the magnetic properties and structures of binary systems involving the rare earths. In a previous paper' some of the magnetic properties of such systems were reported briefly. We have also reported2 a number of compounds of the CusCa type. The compounds were prepared by induction melting in Argon atmosphere of mixtures of stoichiomet-ric amounts of the constituent elements.* For most of the compounds fused alumina or silica crucibles were used as the containing vessel; graphite crucibles were used to prepare CeA12, NdAl2 and TbA12. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis-type Norelco cameras of 114.6 mm diam. The compounds AB2 belong to space group Fd3m-Ol with 8A in a): (000; 01/2 '/2;3) + 000-; b % XA and 16B in dl: (000; oVa %; 3) + 5/87; % %; 7e % Vs\£>. Because the intensities of the reflections on the powder photographs of the different compounds are similar, relative intensities were computed only for DyMnz for CrKa radiation, Table 11. In the calculation of intensities, the Thomas and umeda3 atomic scattering factors, corrected for dispersion,4 were used. The agreement between observed and calculated intensities leaves little doubt that DyMnz has the MgCuz structure. Crystallographic data for the ABz compounds are given in Table JII. Twelve of these compounds have been reported by other authors. A comparison of the published results with our work is given in Table W.* ers of elements of lower purity, to peritectic reactions in some cases, and to the presence of homogeneity ranges in these alloys, so that melting losses would still result in single phase alloys. The possibility of existence of homogeneity ranges in these compounds was investigated systematically only for GdMnz. At room temperature, the solid solution range is between

Jan 1, 1961

By Nicholas J. Grant, H. C. Chang

EMPHASIS on the importance of grain boundary sliding as a mode of deformation at elevated temperatures has been presented elsewhere.' The extent to which boundary sliding occurs under certain creep conditions has been determined for high purity aluminum2,3 and aluminum alloys.' In general, boundary deformation extends quite far into the adjoining grains, resulting in a rather wide band of deformation along the grain boundaries. This has led some investigators to doubt that grain boundary sliding consists of shearing along the boundary surface; it has been contended instead that boundary sliding is a result of concentrated slip in the neighborhood of the deformed grain boundaries."' The purpose of this note is to present evidence that grain boundary sliding takes place by a bulk shear process. gh purity polycrystalline aluminum, wherever and whenever there is grain boundary sliding, boundary migration and concentrated deformation along both sides of the deformed boundary are associated with it. Therefore, it has been rather difficult to obtain unambiguous evidence of boundary sliding. On the other hand, it would be expected in certain alloys of aluminum, when tested under particular conditions. that the severity of the interfering effects of boundary migration and concentrated deformation along the deformed boundary might be reduced. Current research in this laboratory' shows that a 20 pct Zn-A1 solid solution alloy fractures in an intercrystalline manner during creep at 500°F with a small total elongation of not more than about 14 pct, and that it does so with extremely limited grain boundary migration. Accordingly, this alloy was chosen for the present study. The experimental procedure was similar to that used in previous work and has been presented elsewhere.' Two parallel flat surfaces were milled from a round specimen. The gage portion of the specimen was 1 in. x .09 in. x .17 in. The specimens, which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar. The specimens were subjected to creep at 500°F at stresses of 2000 to 5000 psi. The rupture times were from 10 sec to 3 hr. Appreciable boundary sliding occurred in all the tests. A typical example of boundary sliding is shown in Fig. 1. (The tension axis is vertical in the micrographs.) Sliding has taken place along the boundary between grains A and B unaccompanied by important boundary migration. The sharpness of the offset at the triple point can be clearly seen in grain C. As a result of sliding along the boundary between grains A and B, a new boundary surface between grains A and C was created. The offset at the triple point is about 0.07 mm. This boundary sliding is accompanied by the formation of rather sharp kinking bands and, of course, slip on several slip systems in grain C. This type of deformation has been referred to as fold formation' in previous work with high purity aluminum.

Jan 1, 1957