Search Documents

By J. H. Bechtold, R. Kossowsky

1 HE superplastic behavior of the eutectoid A1-78 wt pct Zn alloy has been thoroughly investigated by Back-ofen et al.' The superplastic elongations and the marked resistance to necking were rationalized in terms of high strain rate sensitivity. In a subsequent paper2 superplastic behavior was formulated to show Nabarro-Herring diffusional creep as rate controlling at low strain rates, giving way to a dislocation climb process at higher strain rates. In a paper devoted to an interpretation of superplasticity in two-phase alloys, Packer and sherby3 have included the results of an examination of the structure of an Al-Zn eutectoid specimen before and after superplastic deformation. No significant change in grain size or directionality was observed in the deformed microstructures. This one observation led the authors3 to suggest that con- tinuous recrystallization or grain boundary migration was responsible for superplasticity. The purpose of this note is to report our observations on the superplastic behavior of the Al-Zn eutectoid alloy which differ in certain respects from works previously reported. Following Hayden et al., the results are discussed in terms of dislocation climb as the important factor during superplastic deformation. A heat of nominally high (99.995) purity 22 wt pct A1-78 wt pct Zn was induction-melted and cast into a 0.5 by 6 by 12 in. slab. The slab was heated to 350°C and rolled to 1/8-in.-thick plate. The plate was then cold-rolled to 0.040-in. thickness, annealed at 35OaC, and rolled to the final thickness of 0.020 in.* Speci-

Jan 1, 1969

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10-5 cm. in size.

Jan 1, 1940

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10 5 cm. in size.

Jan 1, 1940

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962

By R. M. Raymond

RECENTLY one of the Welsh coal companies, which has an excellent plant of up-to-date ma-chinery both on the surface and underground, operated under modern methods, sent one of its engi-neers to the United States to study actual operations in the mines. He visited several of the most important and best conducted collieries, went back, and reported that the greatest difference between operations in England and in the United States was. the closer con-tact between management and workmen. By manage-ment he meant management all the way through; close cooperation between office management, superintend-ents, foremen, shift-bosses, etc., and the workmen. A visit to some of the coal mines in that country by the writer made this fact rather impressive. The feel-ing on this side of the water that the methods in use in the coal mines in England are not up-to-date was found in many cases to be quite erroneous. Many mines, particularly those with very thin beds, in which profitable operations are doubtful under the best con-ditions, have necessarily had to adhere to old methods instead of making mechanical improvements. The Powell-Duffryn mines, in the center of the South Wales district, are certainly operating successfully, and have planned their business excellently. Sufficient areas of contiguous land have been leased for extended opera-tions. Mine plants are laid out in the valley, for work-ings on both sides, on a reasonable tonnage of 1500 to 3000 tons to each operation. The beds are from 30 to 48 in. thickness, and a 3-ft. seam is considered an ex-cellent thickness of coal; in fact, the miners prefer to work on the thinner beds rather than the thick ones, where they consider it more difficult to control the backs. This company is making use of its fine coal for produc-ing electric power, which is distributed to its own operations, and for use in the communities adjoining. For this purpose methods of cleaning the fine coal are being put into use. Compressed air is generated at the central power plant and is transmitted over long dis-tances to various mines in each valley. A byproduct coke plant uses more of the fine coal and gives further returns from non-commercial coal. The long-wall system applied in sections of limited size is popular in working the small seams, and me-chanical cutting is used, also handling either by shaking chutes or belt conveyors, or a combination of both. In some mines mechanical cutting is not necessary. The backs are so handled that in the softer or somewhat crushed seams hand cutting can be carried on effec-tively.

Jan 10, 1927

By Robert Linton

Tats paper deals with work that has been carried on for over three years by the management and staff of the North Butte Mining Co. in an effort to standardize mining methods, to eliminate lost motion in the operating organization, and to improve the efficiency of the individual workman. Naturally, much of this work is an adaptation of ideas suggested by other mining operations or by practice in manufacturing and other productive industries. The studies, however, have developed some features that it is believed are new. Both new and adapted features are given in detail. The normal capacity of the North Butte mines is about 2000 tons per. day. Hoisting is done principally through the Granite Mountain shaft, which is 3740 ft. (1140 m.) deep and equipped with an electric hoist capable of hoisting 200 tons per hour from a depth of 4000 ft. (1219 m.). The lowest stoping level is the 3400-ft. The Granite Mountain shaft is connected with the Speculator shaft, about 850 ft. (259 m.) south, and with the Gem, about 1150 ft. (350 m.) east, which are 3000 (914.4 m.) and 2000 ft. (609.6 m.). deep, respectively. These two shafts are equipped with reversible fans for ventilation. The Speculator has a; steam hoist with a capacity of 150 tons per hour from the 3000-ft. level. The Granite Mountain shaft is concrete lined from the 1600-ft. to below the 3000-ft. level and gunited with cement from the 1600-ft. level to the surface. Sections of the Speculator shaft with a total combined length of 500 ft. (152.4 m.) are also concreted. There are approximately 36 miles (58 km.) of drifts and crosscuts in the mine, in which there are 15.2 miles (24.5 km.) of track. At normal capacity, about 75 stoping faces, 20 raises, and 30 sill development faces are working. Stoping is usually by the standard square-set method. Where the size of the oreshoot and character of. the walls permit, the rill (or cut-and-fill) system is employed.

Jan 8, 1920

By H. H. Klepfer, K. J. Gill, P. Chiotti

SOME observations relative to the U-Zn system have been made by other investigators. Chipman1 and Carter2 have reported the preparation of several U-Zn alloys and point out that these alloys are generally difficult to prepare. Chipman1 reported evidence for a high melting compound at about 90 atomic pct Zn and the possible existence of a eutec-tic between the compound and uranium. Raynor," in a theoretical discussion of the alloying properties of uranium, included zinc among the elements predicted to have little or no solubility in a, p, or y uranium. In the present investigation, thermal analyses, X-ray, metallographic, and vapor-pressure data were obtained to determine the phase boundaries. The relatively high zinc pressure over most of the alloys at temperatures of 900 °C and above proved troublesome and special techniques had to be employed in preparing suitable alloys. Materials and Preparation of Alloys The metals employed in this investigation were Ames Laboratory biscuit uranium containing less than 500 ppm total impurities and Bunker Hill slab zinc or Baker Analyzed reagent granulated zinc, both with a purity of 99.99+ pct. Due to the high vapor pressure of zinc and the high reactivity of both uranium and zinc with oxygen at only moderately high temperatures, alloys were prepared in closed containers which had either been evacuated or evacuated and filled with helium. High purity magnesia, magnesia containing 10 pct calcium fluoride, and tantalum proved to be suitable crucible materials. Tw-o different procedures, described below, were used to prepare alloys, the latter being the most satisfactory. The metals, uranium turnings and granulated zinc, were cleaned with dilute nitric acid, rinsed, dried, and placed immediately in a helium-fill'ed dry box. The two metals were placed' in a 10 mil Ta crucible. The charge was enclosed in the tantalum crucible by welding on a preformed tantalum cap. This assembly was enclosed inside a stainless steel (AISI 309) bomb. The bomb was made by welding a piece of stainless steel plate on each end of a stainless steel pipe. All these operations were carried out in a helium atmosphere. These assemblies were heated in a muffle furnace at temperatures between 1100" and 1200°C for 10 to 15 min or held as long as 15 to 20 hr in the 950" to 1000°C temperature range before quenching. Spectrographic and chemical analyses showed no tantalum pickup by the alloys, indicating no reaction between the alloys and the crucibles. However, some of these crucibles failed, probably due to imperfections in the welds of the stainless steel or tantalum crucibles. The second and most satisfactory method was to prepare the alloys by powder metallurgy techniques. The procedure was to press degreased and acid-etched uranium turnings with granulated zinc into 20 g compacts under 20,000-psi pressure. The compacts were placed in MgO crucibles, and sealed in evacuated Vycor or fused silica tubes. The alloys were then heated as long as two weeks at about 550°C in a muffle furnace. The pressed compacts were observed to expand by several volume percent during heating and it was necessary to make allowances for this expansion in order to avoid breaking the crucible and Vycor tube. This method was found very satisfactory for preparing alloys which were suitable for thermal analysis or vapor pressure studies. Experimental Methods and Results The phase diagram for the U-Zn system at 1 atrn pressure, shown in Fig. 1, is based primarily on vapor pressure measurements and on thermal analysis taken at temperatures below 950°C. Fig. 2 shows the U-Zn diagram at 5 atrn pressure, constructed on the basis of thermal analysis of alloys in sealed containers up to 1150°C and on the basis of metallographic, X-ray, and analytical data. The alloys sealed under vacuum were actually under their own vapor pressure and those sealed in an atmosphere of helium were under an additional pressure due to the helium. At temperatures up to 1100°C the zinc pressure is 5 atrn or less for these alloys; consequently the maximum pressure over the alloys sealed under a helium atmosphere was 10 atrn or less at temperatures up to 1100°C. Changes in pressure of this order of magnitude do not appreciably alter the position of most solid-solid or liquid-solid phase boundaries. In constructing the phase diagram for a pressure of 5 atm, the effect of pressure on all phase boundaries except those for liquid-vapor or solid-vapor regions was considered negligible.

Jan 1, 1958

(Under this heading will he published notes sent too the Secretary of the Institute by members or other persons introduced by members.) Management or superintendency desired by member, graduate mining engineer of large practical experience in the details of mining, milling, concentration and cyaniding. Experienced in the efficient mechanical equipment and operation, and in the general business management of a mining property. No. 444. Metallurgist and operator who has specialized in the hydrometallurgy of. gold and silver, particularly stamp milling and cyaniding, desires change from present position. Ten years' experience in Western U. S. Thirty-six years old, married, in best of health and will go. anywhere. Available in 30 days. No. 445.

Jan 4, 1918

By John Mathews

CERTAIN physical and chemical properties of copper are so intimately related that a change in variation of the physical properties indicates a certain chemical change. The standard specifications of copper of the American Society for Testing Materials are based upon physical characteristics with one exception, namely, the copper contents. The physical standard includes electrical properties, defects in the "set or casting," variation in dimensions, weight, etc. Paragraph 4 of the specifications states, " Wire bars, cakes, slabs and billets shall be substantially free from ;shrink holes, cold sets, .pits, sloppy edges, concave tops, and similar defects in set or casting." Shrink holes and concave tops indicate both physical and metallurgical defects; cold sets, sloppy edges, etc., indicate physical defects only; small pit holes may be indicative of either or both physical and metallurgical defects, depending on conditions under which they originated. To the refiner, a copper casting, no matter how made, is known as a "shape," irrespective of whether it is wire bar, ingot, cake, slab, billet, etc. As practically all shapes are cast in an open mold, that is a mold without cope, the surface of the shape cools in contact with the atmosphere and has a coating of oxide. Certain phenomena of the surface indicate the adaptability of the metal for forging or rolling. The writer believes that it is much simpler to produce shapes that are metallurgically correct than those that are mechanically satisfactory. When copper is to be rolled into thin sheets or drawn into very fine wire, the slightest physical defect becomes evident. It is, therefore, of the utmost importance to, consider every characteristic of the shape and ascertain the physical and chemical relationship. Pitch and Set.-The appearance of the surface of the copper when cooled is considered as to its "pitch," or the general contour of the surface of the shape (which may vary from a concave to a convex); and the "set," or the detail appearance of the surface of the shape (the wave-like struc-

Jan 2, 1920

By Frank Antisell

CERTAIN physical and chemical properties of copper are so intimately related that a change in variation of the physical properties indicates a certain chemical change. The standard specifications of copper of the American Society for Testing Materials are based upon physical characteristics with one exception, namely, the copper contents. The physical standard includes electrical properties, defects in the "set or casting," variation in dimensions, weight, etc. Paragraph 4 of the specifications states, " Wire bars, cakes, slabs and billets shall be substantially free from ;shrink holes, cold sets, pits, sloppy edges, concave tops, and similar defects in set or casting." Shrink holes and concave tops indicate both physical and metallurgical defects; cold sets, sloppy edges, etc., indicate physical defects only; small pit holes may be indicative of either or both physical and metallurgical defects, depending on conditions under which they originated. To the refiner, a copper casting, no matter how made, is known as a "shape," irrespective of whether it is wire bar, ingot, cake, slab, billet, etc. As practically all shapes are cast in an open mold, that is a mold without cope, the surface of the shape cools in contact with the atmosphere and has a coating of oxide. Certain phenomena of the surface indicate the adaptability of the metal for forging or rolling. The writer believes that it is much simpler to produce shapes that are metallurgically correct than those that are mechanically satisfactory. When copper is to be rolled into thin sheets or drawn into very fine wire, the slightest physical defect becomes evident. It is, therefore, of the utmost importance to, consider every characteristic of the shape and ascertain the physical and chemical relationship. Pitch and Set.-The appearance of the surface of the copper when cooled is considered as to its "pitch," or the general contour of the surface of the shape (which may vary from a concave to a convex); and the "set," or the detail appearance of the surface of the shape (the wave-like struc-

Jan 1, 1920

By G. H. Wigton

The oxidized ores of the Chief Consolidated Mining Co., in the Tintic mining district, have never yielded to metallurgical treatment by any standard method except smelting. These ores occur in comparatively small, irregular, siliceous replacements in limestone, and carry silver, lead, and gold as the principal valuable metals. But smelting methods are unsatisfactory, as the lead smelters heavily penalize the largc amount of silica in the ore, and the copper smelters do not pay for the lead in the ore; therefore, an alternative treatment method was sought. In 1916, a metallurgical research department was organized under the direction of the writer. Many standard metallurgical methods were investigated but, on oxidized ore, none yielded extraction great enough to make its use feasible. During some chloridizing-roasting experiments in 1916, made in an assay muffle, the writer noted that large proportions of the silver, lead, and gold were volatilized from certain oxidized ores. The possibility of volatilizing the metals and collecting them in the form of a concentrated fume was then studied. But, as it was shown that satisfactory chloride-volatilization would be limited to a furnace feed with a high fusing temperature of the non-volatilizable constituents, and as the results obtained in a rotary kiln with the admixture of common salt with the ground ore were inferior to muffle tests, further volatilization experiments were discontinued until 1920. During this internal, an expcrimental sulfidizing and flotation plant was operated. After the cessation of attempts to float the oxidized minerals, chloride-volatilization experiments .were resumed. The highly infusible flotation tailing from the operation of the flotation mill was used for furnace feed. The first tests made on flotation tailing mixed with 10 per cent, common salt showed nearly complete lead and gold volatilization but considerably less volatilization of silver than in muffle tests. In attempts to increase the silver extraction, the percentage salt in the furnace feed was varied, and it soon became apparent that the use of smaller percentages of salt raised the fusion temperature of the furnace charge and thus

Jan 1, 1926

By Eugene Guccione

"All engineering societies should encourage and motivate their members to take part in public affairs. And engineers, in turn, should learn to translate their technical knowledge in a language which politicians can understand," stated James Boyd last month as he received the Hoover Medal, which is awarded annually by four engineering societies-AIME, IEEE, ASME, and ASCE-to an engineer who has rendered important public service. James Boyd is no ordinary engineer (see box). A few weeks ago, Dr. Boyd took time out of his busy schedule to stop at MINING ENGINEERING'S editorial office for the following exclusive interview.

Jan 1, 1976

By William Y. Warren

Messrs. Thomas & Cross, having leased from the Akron Cement Company from twelve to fifteen acres of abandoned cement-tunnels and chambers, for the purpose of propagating mushrooms for the market, commenced operations about a year ago, and are now beginning to furnish mushrooms in quantities to the local markets of Buffalo and Rochester. The quarries, or, more properly, the mines, of the Cement Company are located at Akron, Erie County, PIT. Y. The cement-rock occurs in a stratum about 71/2 to 8 feet in thickness, which is overlain by from 1.5 to 25 feet of limestone and flint-rock. There is a gentle rise from the opening of the tunnel inwards, giving a natural drainage and leaving the chambers comparatively dry. The roof is good and is supported by pillars and heavy timbers. The mushroom-beds are located about 300 feet from the opening of the tunnel, and are made in the form of mounds about 3 feet by 12 feet, at the base, and 24 feet high, giving to the chambers the appearance of a subterranean graveyard. Many experiments have been made to determine the best form for the beds, and the mound

Jan 1, 1889

By T. Reed Scollon

With some uncertainty as to the type, rate and scope of adoption of air pollution control regulations, and with limited information on the availability of low-sulfur fuels, it is possible at best to make only a rough assessment of the impact of such regulations on coal. It is apparent from the following discussion that regulations of the type already effective or being considered, if adopted and enforced on a widespread basis over a short-term period and if substitute fuels were available, both quantitatively and economically, could result in a loss of more than one-half of coal's markets. Depending on the areal sequence of adoption of such regulations, some areas would be able to obtain limited amounts of low-sulfur coals. Others would not. Because of the usually greater distances from the large industrial coal consuming areas to new sources of coal supply, and because of the higher mine prices for low-sulfur coals, the delivered prices of such coals as might be available would be much higher than those for high-sulfur coals. A large and sudden demand for low-sulfur coals would exert further upward pressure on prices.

Jan 1, 1970

By Frank H. Armstrong

All the mining machinery of the Penn Iron Mining Co. has been operated by electric power for several years and when another shovel for stockpile loading was required the advantages of an electric shovel were naturally considered. After considerable study, serious objections suggested themselves the use of a shovel operated directly by electrical apparatus by reason of the complicated control, severe service on the motors and the heavy surges of current required from the line. It was finally decided to construct an electro-hydraulic shovel using water under pressure to perform all the necessary operations except that of propelling, for which a separate motor was best suited. A car body with boom, dipper handle and dipper of late design, but without any of the steam machinery, was purchased. A motor-driven centrifugal pump, a pressure tank, an air tank, a small air compressor and water cylinders with plungers, pistons and valves, were installed in place of the steam equipment. Fig. 1 shows this shovel under construction and Fig. 2 shows it as it was operated during the first year, the summer of 1914. The large tank at the back of the car, in Fig. 1, carried air under

Jan 1, 1916

By J. E. Burke, A. M. Turkalo

IN 1923 Desch¹ pointed out that the grains in a metal which is anisotropic with respect to its thermal coefficient of expansion would contract differently upon cooling, and that the stresses developed might approximate the plastic strength of the metal. More recently Boas and Honeycombe2-5 studied the behavior of several metals upon thermal cycling and observed that the stresses developed in arlisotropic metals are great enough to produce slip lines in individual grains and a roughening of the specimen surface. This phenomenon they have named "thermal fatigue." The mechanism they propose involves essentially a kneading of the grains, the deformation being alternately in compression and tension in a given grain as the temperature is changed in one direction and then the other. The present work was undertaken to investigate the possibility that an additional mechanism might operate to produce plastic deformation during thermal cycling—a "thermal ratchet" that depends upon a combination of grain boundary flow to relax the stress that develops between differently oriented grains upon raising the temperature and transcrys-talline slip to relax the oppositely directed stress which develops on lowering the temperature. Thus, thermal cycling should produce a nonreversible distortion such that certain grains will change shape differently from their neighbors with a simultaneous displacement being produced at the grain boundary. Temperature Dependence of Grain Boundary and Grain Strength The critical resolved stress for the initiation of slip in metal grains is only mildly affected by temperature." For example, in cadmium it decreases from 0.15 to about 0.05 kg per sq mm when the temperature is increased from 20° to 458°K and further temperature increase causes little further decrease. On the other hand, the work of KG1 indicates that the grain boundaries behave in a viscous fashion that can be described8 by the expression: t = BVexp(Q/RT) [1] t is the shearing stress on the boundary; B, a constant; V, the flow rate at the boundary; Q, the activation energy for grain boundary flow; R, the gas law's constant; and T, the absolute temperature. Eq 1 indicates that the stress necessary to cause a given grain boundary flow rate, V, decreases rapidly with increasing temperature. The value of the constant B is such that at sufficiently low temperature and ordinary strain rates deformation will occur preferentially by slip rather than by grain boundary flow. There is considerable evidence to indicate Consider the bicrystal shown in Fig. 1. In grain 1 the slip plane lies 45 " to the boundary while in grain 2 the slip plane is 90" to the boundary. The coefficients of expansion of the grains in a direction parallel to the length of the crystal are a1 and a, with a, > a2 for the orientations shown. The sequence of events that can occur upon heating and cooling this specimen is illustrated schematically in Fig. 2. Initially there is assumed to be no stress in the specimen (A). Upon heating, grain 1 attempts to become longer than grain 2, but is constrained by grain 2. Thus grain 1 is loaded in compression and grain 2 is loaded in tension, and a shearing stress is present across the boundary (B). As the temperature is increased, the stress will build up, and finally grain 1 will be plastically deformed by slip, since the greater stress is resolved on its slip planes. Any further heating will result in more slip and the stress will remain constant until some temperature T* is reached where the stress can be relaxed by grain boundary flow.† At this relaxation temperature (C) a step will appear between grain 1 and grain 2. Further heating above T* will cause grain 1 to become relatively longer, but no stress will appear because the grain boundary is too weak to support the stress (D). Upon cooling again, at T* (E), the grain boundary will again be able to support a shearing stress, and upon cooling further, grain 1 will be loaded in tension and grain 2 in compression (F). When the decrease in temperature below T* is sufficient to impose the critical shear stress upon the slip plane of grain 1, it will be stretched by slip.

Jan 1, 1953

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By P. Chiotti, J. T. Mason

Thermal, X-ray, metallographic, and resistivity data were obtained to establish the phase diagram for the Yb-Zn system. Six intermetallic compounds and five eutectics have been identified. The compounds position at 695°C. No evidence for the compound YbZn,, was observed. Whether this compound is stabilized or inhibited by small amounts of impurities is uncertain. SEVERAL aspects of the Yb-Zn system have been reported in the literature. Much of this work deals with the crystallographic identification of some of the compounds. The YbZn compound has been reported by Iandelli and palenzonal and the YbZn, structure and thermal data for the composition range between YbZn and Yb3Znll have been reported by Michel et al. A compound of uncertain stoichiometry in the range 60 to 68 wt pct Zn with a cubic structure has been reported by Kuz'ma et aL4 The YbzZn17, YbZn,,, and YbZn13 compounds have been reported by both Kuz'ma et a1 and Iandelli and Palenzona.' YbnZn17 has also been identified by Laube. This investigation was undertaken to establish the phase diagram of this system. Ytterbium in many respects behaves as an alkaline earth rather than a rare earth metal6 and it is of interest to note the resemblance between the Yb-Zn system, the Ca-Zn,' and typical rare earth-zinc systems.g'10 MATERIALS AND EXPERIMENTAL PROCEDURES The materials used in this investigation were Ames Laboratory ytterbium and Bunker-Hill slab zinc, 99.99 pct pure. Analyses of the ytterbium showed 38 ppm Ta, 82 ppm 0, and 15 ppm N with Ca, Cu, C, Mg, Al, Si, Cr, Fe, Ni, Sc, Y, Er, Tm, and Lu all less than 50 ppm. The ytterbium was dehydrogenated by heating in tantalum under vacuum for 8 hr at 900°C. The metal was kept under argon except when being cut with shears and when being weighed. Tantalum was found to be a suitable container for alloys in the composition range between ytterbium and Yb2Zn17. With higher zinc concentrations the tantalum was penetrated by the alloy and failed after several days at temperatures of 600" to 700°C. Approximately 20 g of zinc and ytterbium metal were sealed under argon in *-in.-diam tantalum cruci- bles equipped with thermocouple wells. The crucibles were in turn sealed in stainless-steel jackets. The alloys were equilibrated in an oscillating furnace and given various heat treatments in a soaking furnace. The steel jackets were removed and differential thermal analysis data were obtained under an atmosphere of argon. The thermal analysis apparatus was calibrated against the melting points of pure zinc, aluminum, silver, and copper and found to give thermal arrests within 1°C of the accepted melting temperatures for these elements. The thermal analysis apparatus has been described in an earlier paper.g Alloys were further heat-treated as necessary and subjected to metallographic examination and X-ray diffraction analysis. Most alloys were etched with Nital (0.5 to 10 pct nitric acid in alcohol). EXPERIMENTAL RESULTS The results of the thermal analysis are summarized by the points on the phase diagram, Fig. 1. Six compounds and five eutectics were observed. The eutectic temperature and compositions in weight percent zinc are 491°C and 12 pct, 645°C and 32 pct, 687°C and 54 pct, 742°C and 67 pct, and 750°C and 77 pct. The compounds YbZn, YbZn2, Yb2Zng, Yb2Zn17, and YbZnll melt congruently at 650°, 751°, 75Z°, 754", and 755"C, respectively. The compound Yb3Znll undergoes a peritectic decomposition at 695°C. The transformation and melting temperatures for the ytterbium were observed to be 797" and 817°C. re-

Jan 1, 1969

By J. L. Giove, J. M. Hodge, R. G. Storm

The hardenability effect of molybdenum has been evaluated by a number of investigators, including one of the present authors.1,2,3,4,6 Considerable discreMncy exists, however, among the results of these various investigators, and two of them, Brophy3 and Kramer,4 have indicated that the apparent hardenability effect of molybdenun would vary, depending upon the other alloying elements in the steels being considered. The results of previous, unpublished work conducted at the Duquesne Works Laboratory of the Carnegie-Illinois Steel Corporation also have indicated significant differences in the hardenability effect of molybdenu~n in nickel and in chromium steels. The present investigation was undertaken in an effort to establish the mechanism governing this difference in the hardenability effect of molybdenum. This work involved both end-quench hardenability and isothermal transformation tests on two series of steels of varying molybdenum content. One steel contained 3 pct nickel and the other 1 pct chromium. It was hoped that such studies would shed further light on the mechanism of this behavior. Materials and Experimental Work MATERIALS The chemical compositions of the steels used in this investigation arc shown in Table 1. These steels were furnished by Battelle Memorial Institutc in the form of 100-lb induction furnace ingots. The top half of each ingot was forged to 1 3/8-in. square billets and then rolled to I-in. round bar stock for isothermal transforma- tion studies. The bottom half of each ingot was forged into approximately 1 1/4-in. rounds for end quench tests. All of the steels were normalized from 1650°F and tempered at 1100°F before nlachming to end quench or isothermal samples. END-QUENCH TESTS standard l-in. diam end-quench tests were made on each of the steels. The test bars were austenitized at 1600°F for 30 min,, quenched in a standard Jominy jig, and hardness surveys were made in all tests. The 95 pct martensite point was deterInined from hardness values5 and cheeked by metallographic examination. The jominy distance values for 95 pct martensite were converted to hardellability values in terms of ideal diameter (Dl), using a revised carve for the relationship between Jominy distance and ideal diameter. This curve was based on the cooling time from the A1 to the bainite nose temperatures rather than on the usual criterion of half-temperature time. The cooling rates as determined by Russell and Williamson9 were used as a basis for this relationship. The derivation of this curve is described in detail in the appendix. ISOTHERMAL TRANSFORMATION STUDIES Samples for the isothermal transformation studies were quarter sectors of 1/16.is-in. thick slices from the 1-in. round bars. All samples were austenitized for a total the of 15 min., transferred rapidly to a lead bath for isothermal transformation, and brine quenched from the lead bath. A time of 3 see was allowed for the sample to come to the temperature of the lead bath, and this time was not included in the isothermal transformation times. Each sample was examined metallo-graphically at a magnification of 100 diam. The per cent transformation was estimated by comparison with standard micrographs, and the values were plotted against the on log/log coordinate paper. At least 4 and as Inany as 10. points were plotted for each steel. A line was drawn through the points for each steel, and the times for 5 pct transformation were obtained from the plot for each steel. Isothermal transformation diagrams in terms of 5 pet total transformation, covering the temperature range of 800 to 1200°F, were determined in this manner for an austenitizing temperature of 1600°F. The times for 5 pct transformation at the bainite nose for austenitizing temperatures of 1800 and 2000°F were also determined in the same manner. These times for 5 pct total transfor-

Jan 1, 1950

By Neville G. W. Cook

The ultimate goal in rock mechanics is to make quantitative predictions of the response of rock to changes. Measured and calculated values of changes in displacements or temperatures in the rock for six different field experiments are compared using linear regression. When values of the mean compressive stresses are large compared with the values of the deviatorial stresses, linear elasticity, using values for Young's modulus from laboratory tests, provides a good predictive model. However, if the values of the mean compressive stresses are small compared with those of the deviatorial stresses the behavior and response of the rock, though systematic, is not linear. Linear heat conduction provides good predictions of changes in rock temperatures but thermal displacements are not predicted well by linear thermoelasticity.

Jan 1, 1982