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By R. D. Carpenter, R. R. Smith, E. E. Sougstad

The Union Carbide Nuclear Co., in treating low-grade tungsten and molybdenum-copper ores at the Pine Creek mill near Bishop, Calif., employs flotation for the initial extraction of the valuable mineral constituents. These minerals consist of scheelite, molybdenite, and several of the copper sulfides including chalcopyrite, bornite, and possibly chalcocite. They occur in a gangue consisting mainly of quartz, pyroxene, and garnet, with minor amounts of calcite and fluorite. This assemblage of minerals presents an unusual grinding problem because of their diverse physical characteristics. Feed for the circuit is prepared from -6-in. ore by screening on a rod deck screen to remove the -5/8 - in. material. The+5/8-in. fraction is crushed in open circuit with a 5 1/2-ft Symons shorthead crusher operated at a closed- side setting of approximately 3/8 in. The screen undersize and the conecrusher discharge are then combined to constitute the feed to the grinding circuit. The ore is ground in 6 by 5-ft grate discharge ball mills operated in closed circuit with 54-in. spiral classifiers. The classifier overflow goes directly to the flotation section of the plant. Studies of the flotation circuits have shown that the maximum recovery of the tungsten, molybdenum, and copper minerals occurs in the particle-sue range from 100 mesh to approximately 400 mesh. Further, practice has shown that the ore minerals are effectively reduced to this size range if the total ore is ground to -48 mesh. The general objective of the grinding circuit then is to reduce the feed to -48 mesh with the production of a minimum amount of slimes. The purpose of this investigation was to ascertain how well the grinding circuit was carrying out this objective. The method used was to sample the various products in the grinding section, size these products accurately, and analyze the resulting sue distributions. SAMPLE PREPARATION AND SIZING TECHNIQUES Representative samples of the different grinding circuit products, namely, new feed to the ball mill, ball mill discharge, classifier overflow, and classifier return, were taken over a 24-hr period. The samples were then dried without being filtered to avoid loss of slimes. The percentages of solids in the different products were the following: new ball-mill feed, 95%; ball mill discharge, 82%; classifier overflow, 52%; and classifier return, 84% solids. Particle sizes were determined on each product by wet-screening an

Jan 1, 1962

By Basil B. Zavoico

CRUDE oil production in the United States during 1938 reached approximately 1,214,355,000 barrels, an average of 3,327,000 barrels per day, or 5 per cent below the 1937 record output of 1,279,160,000 barrels. The decreased production did not prevent the stocks of all products from increasing to a total of 575,954,000 barrels by Sept. 30, an increase of 10,957,000 above the total on Jan. 1, or an average daily storage increase in all products of 40,135 barrels. The increase in total stocks was made entirely in the refined products, stocks of crude oil during the first nine months of 1938 having actually declined 7,155,000 barrels to 299,671,000 barrels, or an average daily decline of 26,209 barrels. The 1937 reversal of the preceding five-year trend of discoveries totalling less than withdrawals was continued through 1938 with indicated reserve addition from both new discoveries and extensions considerably in excess of the

Jan 1, 1939

By F. C. Blickensderfer

THE CHAIRMAN (B. B. GOTTSBERGER, Miami, Ariz.).-On your trip today through the Inspiration and Miami mills you have seen in actual operation the machines which represent the changes adopted in grinding methods in the Miami district from the beginning of operations in March, 1911. In one section of the Miami plant are three Chilean mills not yet discarded, representing the first machines adopted. In another section, pebble grinding is still in operation, while in the balance of the plant, pebbles have been replaced with iron balls. In all cases these machines are handling a feed which is the product of roll, grinding down to about ¼ in. in, size. The latest step in grinding in the district, You saw at the Inspiration plant, where in Marcy mills a filed, the larger pieces of which remain on a 2-in. opening, is being reduced in one operation to a product of which only about 3 per. cent. remains on the 48-mesh screen. A detailed comparison of the methods used at the two plants would be very instructive but our own work at Miami has not yet reached a point where such a comparison is possible, the reason being that our final product is not yet fine enough. By means of larger Hardinge mills operating in closed circuit with Dorr classifiers soon to, be installed in one section of the plant, we hope to obtain, under properly balanced operating conditions the same end result as at Inspiration. It, might interest you, however, to know some of the results we have obtained here by the substitution of balls for pebbles. With pebble grinding, using three 8-ft. by 22-in. mills, followed by one 8-ft. by 66-in. mill for regrinding the coarse product of the primary mills, we handled 636 tons per 24 hr. in one section of the plant. Substituting balls for pebbles in the first operation and using two mills in place of three we obtained a tonnage of .714 tons to the section. With the use of balls both in the primary mills and in the regrinding mills, the tonnage for one section was raised to 822 tons per day. Coincident with this increase in tonnage, we also obtained a greater efficiency. The use of pebbles in all mills showed 21.5 per cent. plus 48-mesh material in the final tailing, which figure was reduced to 13.9 per cent. for balls followed by pebbles, and to 4.6 per cent. with the use of balls both in the primary and regrinding mills.

Jan 12, 1916

By J. Landau, A. Dim, R. Houlihan

Recent developments in the application of solvent extraction in hydrometallurgical processing make it desirable to reassess the present state of availability of suitable equipment for these applications. The range of solvent extraction applications now includes very large scale applications with a modest demand on separation performance (the treatment of some base metals) and applications in which the decisive factor is a very high requirement on separation performance. The extraction column to be described in the present paper is of the type in which mechanical energy is provided for the two- liquid system inside the column. The active elements for this are reciprocating sieve plates designed and mounted so as to uniformly load the driving mechanism, to eliminate vibration of the plant, to have sufficient control over the degree of dispersion of the dispersed phase, and to reduce axial mixing effects, which are highly detrimental to the separation performance of production-scale plant. The operating features of the reciprocating-plate column will be illustrated mainly by experimental results obtained on a 4" diameter column in the extraction of uranyl nitrate with TBP. Some mechanical features of the operation of reciprocating-plate columns will also be discussed.

Jan 1, 1973

By Claus G. Goetzel

PRESSING of powdered metal parts is best done in the direction of the shortest extension of the piece, to avoid too great a loss of pressing force through internal [ ] friction. As long as curved surfaces, recesses, or offsets occur only parallel to this shortest axis of pressure, no special difficulties arise: the cross sections, perpendicular to the pressure, do not vary, nor does the shape of the parts change during compression except for a gradually reduced thickness (Fig. IA). The problem becomes more difficult, however, when the curved surfaces or recesses are perpendicular to the shortest axis of the part (Fig. IB). Two processes for molding uniformly dense parts with complicated shapes from powdered metals are described in detail in this paper. Both can be employed successfully by those trained in the art. The first refers to curved parts; the second is especially adapted to parts having one or more recesses or steps. Both methods, as set forth here, are applied under the condition that presents the more difficult problem. For clarity, before description of the two practical methods, the variable factors in molding powdered metal parts will be reviewed, then an idealized procedure will be considered briefly. VARIABLE FACTORS IN MOLDING POWDERED METAL PARTS Compression Ratio Compression ratio is defined as the proportion of the final relative density of the compact to the apparent density of the powder. For iron powder of an apparent density of 3.0, for example, a compression ratio of 2 1/2 : I would be required to produce a compressed compact of 7.5 density; whereas for another iron powder having an apparent density of only I.5, a compression ratio of 5:I would be required to produce the same density. The lower the powder's apparent density, the greater must be the compression ratio for pressing compacts of high density.

Jan 1, 1945

By Henderson, Robert

A GOOD idea of the magnitude of the underground operations at Climax can be gained from the following figures. A little more than 43,000,000 tons has been drawn from the mine and of this amount, 40,500,000 tons has been drawn in the past ten years and 12,000,000 tons was drawn in two of the war years. The maximum daily average output over a period of one month was slightly more than 20,000 tons but during this period, production on certain days was 24,000 tons, and 9000 tons was produced in a single eight-hour shift. This production came chiefly from 260 draw points although all of them were never in operation at one time. The haulage system for these draw points is made up of 7.5 miles of 36-in.-gauge track, and 131,000 ft. of subsidiary drifts and 44,000 ft. of raises have been driven to develop the necessary broken ore reserves for this high production. Power consumption is often considered an index of operating efficiency. In 1943, the year of maximum production, the mine power consumption was 19,223,000 kw.-hr. or 3 kw.-hr. per ton; in 1945 it was 3.5 kw.-hr. per ton. To handle this amount of power, there are four transformer stations and one switch station in the mine. Mr. Garrabrant, the chief electrician, describes the electrical installation in this issue.

Jan 1, 1946

By J. E. Harris, J. A. Whiteman, A. G. Quarrell

The graphitizing reaction has been studied in a number of Fe-C-Si alloys in the temperature range 550° to 725°C. The TTT relationships exhibit "C" curve behavior except where nuclei, either foreign or graphite itself, are present before the start of the reaction. It is suggested that the rate -controlling process is diffusion of carbon through ferrite. For the reaction to proceed at the observed rate it is calculated that the matrix surrounding the particles must deform plastically; experimental evidence for this deformation is presented. It is well-established that the decomposition of austenite to pear lite occurs at a maximum rate at an intermediate temperature.l-5 This "C curve" be- havior, which has been reported in a number of other systems,5-10 is a consequence of the relatively low rate of nucleation of the pearlite at small degrees of undercooling of the austenite. The cemen-tite phase in the pearlite is, in turn, metastable with respect to graphite and if steels are held for prolonged periods at elevated temperatures decomposition of the pearlite occurs. It is difficult to predict the shape of the subcriti-cal graphitization TTT (time, temperature, transformation) diagram for, in this case, undercooling does not occur. However, the free-energy change for the reaction does decrease with increasing temperature" (Fig. 1) and it is thus anticipated that the rate of nucleation will fall as the temperature approaches that of the eutectoid. In addition, a decreasing growth rate with increasing temperature is predicted in some circumstances with pure Fe-C alloys. However, apparently similar conditions exist for first-stage graphitization in the austenite range (malleabilization) but no evidence for C curve behavior has been presented in the extensive liter-

Jan 1, 1965

By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By Frank M. Howell, Claude E. Schmidt

To counteract the spiralling costs of labor and materials against the fixed sale of its product, namely, gold at $35 per oz, Homestake Mining Co. has revised the milling flowsheet once and effected increases in the daily milling rate twice in the past 12 years. During this period the mining department has been able to hold production costs steady by increased productivity through technical improvements and utilization of the most modern mining by CLAUDE E. SCHMIDT and FRANK M. HOWELL, JR. 46-MINING ENGINEERING, APRIL 1963 equipment. The flowsheet alteration occurred during 1951-1953 when the two crushing plants at the shaft head frames were converted to a three-stage crushing system with the third stage closed circuited to produce a minus 5/8-in. product as rod mill feed.

Jan 4, 1963

By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.'-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young's equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young's equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young's equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By Alvin Kaufman

At the turn of the century the U.S. had a gross ALVIN KAUFMAN Mineral Economist U.S. Bureau of Mines area slightly in excess of three million square miles, a population of 76 million, a gross national product of $37 billion (constant 1929 dollars) and a mineral production valued at $2 billion (1929 dollars). Some 60 years later its area had increased by 600 thousand square miles, population had risen 140%, gross national product was seven times greater and mineral production had grown to a value five times that of 1900. Of perhaps greater significance, however, were the changes wrought by technology. It was during this period that the "American Way of Life" was revolutionized by the introduction of the airplane and the automobile; man also took his first probing steps in the utilization of nuclear energy and pre- pared to unlock the secrets of space. It was during these six decades, also, that he learned to create additional new materials, some of which were from old sources such as plastics from petroleum and coal. These new materials have created competition and attendant problems for the traditional materials such as iron, copper, lead and zinc. Additional problems undoubtedly will be created by technologic advances in the future.

Jan 2, 1963

FRED. MACCOY, Raton, N. M. (written discussion *).-In the review of the Chilean nitrate industry presented by Messrs. Rogers and Van Wagenen, the most critical point relating to the future of the industry has been summed up in the last paragraph: when nitric acid can be produced synthetically cheaper than from the Chilean deposits, the Chilean industry will cease. A study of the prevailing mining methods and extraction process leads one to suspect that much can be done to reduce the present cost of the finished product; and a reasonable reduction of the cost would make available immense reserves of low-grade caliche, the locations of which are fairly well delimited. In a study of costs, one finds that actual data are very hard to procure. The average operator does not know, with any degree of reliability, his "head assay," what percentage of the caliche is lost in mining, nor what tonnage of caliche he is putting into the maquina. One manager remarked to me, "We are not concerned in what it costs to treat a ton of caliche, we are interested only in what it costs to, produce a quintal of' finished nitrate." Apart from the crude methods of mining, and the inefficient work in extraction, attention is at once drawn to the fact that the 40d., stated as the cost of the nitrate at the plant, has become 80d. by the time it is on board ship. Of this 100 per cent. increase in value, 70 per cent. is

Jan 4, 1918

By C. Y. Wen, H. O. HOPMAN

l. INTRODUCTION. IN casting a thermal balance of the heat generated and absorbed in a blast-furnace treating lead-, copper- and similar non-ferrous ores, assumptions have always to be made for the values of the heat of formation of slag. ? Considering that the larger part of the charge introduced into the furnace comes out in the form of slag, the significance becomes apparent of a lack of heat-values for the singulo-silicate, which is the type of slags commonly made. The aim of the present investigation is to supply these heat-values as far as possible with the apparatus and the time available. The heats of formation of the ferrous and manganous bi-silicates have been determined by Le Chatelier; 1 those of some silicates other than iron and manganese by Tschernobaeff:2 finally Richards 3 gives a figure for a copper blast-furnace slag of known composition. The existing data and those resulting from the present investigation are assembled in Table VI. II. MATERIALS USED. The materials used in the experiments were silica, ferrous oxide, and calcium carbonate. Silica.-The silica sold in the market as chemically pure usually contains small amounts of magnesia, lime, and alumina, and is therefore not suited for the work. The pure material was obtained from clear quartz crystals from Arkansas, broken in a diamond mortar and ground in an agate mortar to pass 1 Comptes rendus, vol. cxx., p. 623 (1895); vol. cxxii., p. SO (1896). 2 Revue de Métallurgie, vol. ii., p. 729 (1905); Electrochemical and Metallurgical Industry, vol. iv., No. 2, p. 72 (Feb., 1906). 3 Electrochemical and Metallurgical Industry, vol. v., No. 7, p. 266 furls?, 1907;) ; Metallurgical Calculations, vol. iii.,.pp. 474, 475 (1908).

Jul 1, 1910

By L. F. Mondolfo, B. E. Sundquist

The crystallographic orientation relationships resulting when lead is nucleated from the liquid by Ni, Cu, Ag, and Ge were determined. For each nucleating agent several definite orientatioz relationships were found. These relationships seemed to be controlled by good symmetry relations and low crystallographic disregistry between mating planes. For any given nucleating agent the under colling for nucleation was found fairly constant and independent of the orientation relationship and consequent disregistry. It was also found that, upon re melting and refreezing the Pb, the orientation relationship was changed. These findings prove that crystallographic disregistry is not the controlling factor in heterogeneous nucleation from the liquid. The results of this investigation tend to confirm the theory presented in a preceding paper that heterogeneous nucleation starts with the formation of an adsorbed layer of nucleated metal on the nucleat-ing impurity. Evidence is given that cavities in the nucleating agent act as centers of nucleation. IT has long been known' that solid extraneous particles are active in catalyzing phase transformations that occur in a system, particularly condensation and crystallization. It is well established that these heterogeneities act as catalysts by providing surfaces upon which nuclei of the precipitating phase can form with activation energies smaller than those required for homogeneous nucleation. Numerous investigations have shown that in this process of heterogeneous nucleation: a) the nucleus forms with one, or several, definite crystallographic orientation relationships with the nucleating phase2-4 and b) that there is a small range of undercoolings or super saturations characteristic of the nucleation of a given solid on a given Substrate.5-10 Turnbull and vonnegut11 have developed a theory based on theories developed by Volmer12 and Turn-bull and Fisher1= for heterogeneous nucleation from gases and liquids, that relates the super saturation or undercooling required for nucleation to the dis-registry between the lattices of the nucleus and the nucleating agent. This theory predicts that nucleation should occur with the orientation relationship between the nucleus and nucleating agent that minimizes the disregistry. Further, it predicts that the undercooling or super saturation necessary for nucleation should be a function of the disregistry. Numerous investigations have dealt with the orientation relationships resulting from the condensation of vapors onto crystalline solid substrates2,3 and a few with the nucleation of one phase by a second phase in solidification4,14. Others have dealt with the supersaturation8-10 and undercooling5-7 associated with nucleation in condensation and solidification respectively. However, there is virtually no report that gives both of these factors for the same system. In this investigation a study was made of the undercoolings and orientation relationships resulting when Pb is nucleated from the liquid by Ni, Cu, Ag, and Ge. It was the purpose of this investigation to check the Turnbull-Vonnegut theory, i.e., the importance of crystallographic disregistry between nucleating catalyst and nucleated metal. The results indicate that disregistry is not an important factor in nucleation and that the nucleation process is probably somewhat more complex than current theories suggest. EXPERMENTAL PROCEDURE Small single crystals of nickel, copper, silver, and germanium were prepared from materials of four to five nines purity, and the Pb used was also 99.999+ pet pure. Cu and Ag single crystals were prepared by sealing small chips of Cu or Ag in an evacuated quartz capsule and heating the capsule at 2000°F for 1 hr before cooling. Nickel crystals of 200 diam were also prepared in evacuated quartz capsules, but melting was done by heating the capsules in an oxy-acetylene flame for a few minutes. These spheres were invariably polycrystalline so

Jan 1, 1962

By D. C. Holloway

Ceramic projectiles made from 94% to 99% alumina with a nominal mass of 3.1 gms were fired into granite blocks. The average compressive strength of the ceramic was 800 MPa and that of the rock was 135 MPa. Flat, ogive, conical and pyramidal nose shapes were evaluated at velocities ranging from 450 to 1400 m/sec. It was found that the conical and pyramidal nose shapes at the higher velocities did a significant amount of damage to the rock. On the average, they removed 10 5mm3 of rock and were six and ten times better than the flat and ogive nose shapes. It was also observed that increases in volume occur in discrete steps. This process is highly dependent on the ability of the projectile to penetrate the rock.

Jan 1, 1984

By Carl R. Davis

The cost of mining during the past history of these mines has been excessive, principally by reason of the inefficiency of labor under the wage-system. The amount of labor performed per man was unsatisfactory; and Mr. Edmund B. Kirby, the general manager, decided to adopt the contract-system as a remedy. For this purpose the method now in use was devised by the writer (then and now the superintendent), as best adapted to the local conditions. On March 12, 1900, this system was presented to the miners of the War Eagle and the Center Star. The issue remained unsettled for several weeks,

Jan 1, 1902

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By R. D. Reiswig

An increasing amount of high-temperature metall~?~gical research is carried out in resistively heated tube furnaces in which a bare specimen is suspended by a fine wire at the midpoint of the tube. It is shown that the assumption of near-blackbody conditions on the surface of the sample may give rise to errors in optical pyrometry of 50°C or more. A number of papers published in the metallurgical literature in recent years have described the use of high-temperature tube furnaces for heat treatments, melting-point determinations, and other work. Typically, the tube is of a refractory metal with open ends, is heated by the passage of an electric current, and has concentric cylindrical radiation shields outside it. In at least one of these,' the specimen is contained within a crucible having a small hole in its lid through which optical-pyrometer measurements are made under essentially blackbody conditions. In another design,* the specimen is inside a muffle which is concentric with the heater tube and which contains a number of washerlike longitudinal radi- ation shields to reduce axial temperature gradients and to give conditions near the specimen closer to those of a black cavity. Yet another design3 employs a wire specimen coaxial with the heater tube. Blackbody conditions are simulated by passing current from a separate supply through the wire until it "disappears" against the background (the inside of the heater tube) as seen through a radial spy hole in the tube. Good agreement with known melting points is achieved when an optical pyrometer is used under such disappearance conditions as the melting point is approached. That this latter method works so well is due, evidently, to considerations such as those mentioned by Dike4 and others.5-8 A more common method than the above, however, has been the suspension of an uncovered specimen by a fine wire in a resistively heated tube with open ends. A radial spy hole about midway between the ends of the tube permits optical-pyrometer observations on the specimen, the inside of the tube, or both. So observed, the specimen typically appears to differ but little in brightness temperature from the inside of the tube. According to De vos9 the radiation from such a spy hole in an empty tube of reasonable 1ength:diameter ratio (e.g., 10 or greater) should be essentially blackbody radiation. For these reasons, apparently, descriptions of work carried out in such furnaces usually include a statement to the effect that conditions surrounding

Jan 1, 1964

By Bruce W. Gonser, A. U. Seybolt

A few copper-zinc-hasp alloys mppt die-casting requirements reasonably well, although improvements are desired. Aluminum bronzes, high-tin bronzes and some copper-nickel-zinc alloys can be die-cast, according to Herb,' but seldom are because of such factors as higher melting ranges and greater cost than certain of the brasses. Fox2 has summarized the copper-base die-casting alloys that were in commercial use in 1937 and has given the effects of different alloying constituents. Table 1 gives some of the properties of these alloys as reported by Fox. a Properties reported by Fox.2 b Trade name of Brastil, Doehler Die Casting Co., similar to Webert Alloy,34 American Brass Co., and Tombasil Alloy,5 Ajax Metal Co. e Trade name Tinicosil, Titan Metal Manufacturing Co. Melting point (liquidus) of the yellow brass is given by Herb1 as 1650" F., of the high-silicon Brastil (with 4.5 to 5 per cent Si) as 1600" F., and of the nickel silver as 1675" F. d Criterion not stated.

Jan 1, 1940

By A. U. Seybolt, Bruce W. Gonser

A few copper-zinc-hasp alloys mppt die-casting requirements reasonably well, although improvements are desired. Aluminum bronzes, high-tin bronzes and some copper-nickel-zinc alloys can be die-cast, according to Herb,' but seldom are because of such factors as higher melting ranges and greater cost than certain of the brasses. Fox2 has summarized the copper-base die-casting alloys that were in commercial use in 1937 and has given the effects of different alloying constituents. Table 1 gives some of the properties of these alloys as reported by Fox. a Properties reported by Fox.2 b Trade name of Brastil, Doehler Die Casting Co., similar to Webert Alloy,34 American Brass Co., and Tombasil Alloy,5 Ajax Metal Co. e Trade name Tinicosil, Titan Metal Manufacturing Co. Melting point (liquidus) of the yellow brass is given by Herb1 as 1650" F., of the high-silicon Brastil (with 4.5 to 5 per cent Si) as 1600" F., and of the nickel silver as 1675" F. d Criterion not stated.

Jan 1, 1940