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The Institute is still in need of additional copies of the Bulletin for January, February and March, and will be glad to pay members the regular price of fifty cents per copy. Copies may be sent express collect, or postage may be used and the amount will be refunded in addition to the fifty cents.

Jan 10, 1916

By R. G. Weavind

ONE of the most important fields of investigation at the Diamond Research Laboratory in Johannesburg is concerned with improvements in metallurgical practices for the diamond mining companies, with particular reference to increased recoveries of the smaller industrial stones. Considerable work has been done on the possible application of flotation processes to the diamond industry.

Jan 7, 1951

MINING ASSOCIATION, UNIVERSITY OF CALIFORNIA At a meeting of the Mining Association of the University of California, held Feb. 12, officers for the present semester were elected as follows: President, Richard C. Kerr, '19; vice-president, Glen T. O'Brien, '20; secretary, Kenneth V. King, '19; treasurer, Sam Grinsfelder, '20. KENNETH V. KING, Secretary.

Jan 4, 1919

By W. P. Haynes

The 1938 production for all of Rumania amounted to 48.984.200 bbl., as compared with 53.239.500 bbl. in 1937. which represents a drop of 4.255.300 bbl., or 8 per cent. Of the various fields. there are only two major increases in production—Baicoi-Tintea with 3.092.400 bbl. And

Jan 1, 1939

By W. P. Haynes

The 1938 production for all of Rumania amounted to 48.984.200 bbl., as compared with 53.239.500 bbl. in 1937. which represents a drop of 4.255.300 bbl., or 8 per cent. Of the various fields. there are only two major increases in production—Baicoi-Tintea with 3.092.400 bbl. And

Jan 1, 1939

By Harlowe Hardinge, R. C. Ferguson

Laboratory and plant data covering 12 different operations show that lower than "standard" ball mill speeds increase grinding efficiency. In the case of high pulp-level mills, the gain is so great that the increase in capital cost of the larger lower speed mill will pay for itself in less than a year's time.

Jan 11, 1950

Procurement of uranium is vital to the future of the Nation. Its utilization for atomic energy can destroy mankind or raise an unsurpassable civilization-the problem of the statesmen. Uranium poses a challenge to the mining profession. Evanescent in occurrence, its discovery and mining can mean substantial profits, plus safeguarding the future of the Nation.

Jan 9, 1951

By William P. Blake

In view of the present exposition at Atlanta, and the timely meeting of the Institute in that city, and the expressed desire of the Council for contributions to the knowledge of the mineral resources of the Southern States, I may be permitted to offer some desultory notes upon the subject, chiefly in the form

Jan 1, 1896

By Kenneth K. Humphreys, J. W. Leonard, T. S. Spicer

INTRODUCTION Reasons for Thermal Drying The continuing increase in the percentage of - '/4 in. ( -6.3 mm) coal produced as a result of the increased use of mechanical mining methods has, over the years, tended to shift considerable portions of the work of producing salable coal to the fine coal cleaning section of the preparation

Jan 1, 1979

By A. A. Collins

When we speak of high copper on a lead blast furnace we think in terms of 4 to 5 pct, or. any lead charge carrying over 1 pct. Any copper on charge will produce its corresponding troubles such as lead well, extra slag losses, drossing problems, and the working up of the dross. This is indeed a very interesting subject and one that used to give the old-time lead metallurgists such as Eiler, Hahn and lles many worries, not so much in the actual operation of the hlast furnace but in the working up of the copper. When the American nletallurgists commenced with the American rectangular-shaped lead blast furnace in the 1870's and got away from the reverberatories such as were in use in Germany and other parts of the world, they went to greater tonnages, as 80 to 100 tons per day in comparison to the 20 to 30 tons per day in the other processes. With the greater tonnages along with insuficient settling capacity, the silver losses in some cases were increased. Hence the lead-fall was low, for there were no leady concentrates in those days to assist the metallurgist to gain lead or an absorber for the precious metals; and in some cases copper sulphides were added intentionally to the charge to produce a copper matte to lessen the silver losses through the dump slag. The operators in those days thought that where some copper was always present in the lead ores the copper should not enter into the reduced lead and alloy with it. This, by the way, is just the reverse of our present-day practice, when we try to put all of the copper into the blast furnace lead and to remove the same through the drossing kettles. Therefore the furnace was operated to produce a certain amount of matte or artificial sulphides, since, due to the great affinity of copper for sulphur, any copper present would enter the matte almost completely. Thus, the lead bullion produced was practically free from copper. The products of the furnace were metallic lead or lead bullion, containing 05 to 95 pct of the lead and about 96 pct of the silver which were in the ore—a lead-copper-iron matte which contained nearly all the copper in the ore and the slag, the waste product. In the United States, up through the year 1092, we find the small furnace 100 X 32 1/2 in. with 12 tuyeres, some 6 on each side, plagued with a small amount of poorly roasted sulphides— either from heap or hand roasters that produced matte. This matte was roasted and if poor in copper was returned for the ore smelting. Otherwise it was smelted either alone or with additions of rich slags or argentiferous copper ores, the products being lead and a highly cupriferous matte, the latter being subsequently worked up for its copper. The lead metallurgists kept trying and improving on furnace and roasting equipment designs until we find blalvin W. Iles constructing at the old Globe Plant at Denver what came to be the modern furnace. That is, in 1900 he built a furnace of 42 in. width by 140 in. at the tuyeres with a 10 in. bosh and a 16-ft ore column. This type has been more or less standard to the present time, though modified in width and length to meet the demand for large tonnages and improvements in structural details. In 1905 at Cananea, Mexico, Dwight and Lloyd developed the present down-draft sinter machine that has meant so much in producing a well-processed material for the lead blast furnace. In 1912 Guy C. Riddell came forth with double roasting at the East Helena Plant of the American Smelting and Refining Co., which removed the "zinc mush plague." Incidentally, with the introduction of double roasting, which most lead plants were forced into after 1924, when lead flotation came into its own, less matte or no matte was produced. When this stage arrived, the copper was forced into the dross and the casting of lead at the blast furnace lead-wells was stopped. In plants with a fair copper carry 1 pct or better on the blast furnace charge, the lead wells became inoperative once the production of matte stopped. The copper drosses clogged the lead wells and even with bombing, either water or dynamite, the operators could not keep them open. Thus, the lead wells were abandoned in some plants, such as at the El Paso and Chihuahua smelters of the American Smelting and Refinillg Co., and all lead taken out through the first settlers. The elimination of sulphur, espccially sulphide sulphur, from the blast furnace charge and the nonproductiori of matte resulted in a great saving of tinie, energy and equipment in the recirculation of the copper, With the copper content in the dross and dross-fall ranging in quantities from a few percent up to 60 pct, such as at El Paso, a drossing problem was created. As the old-time operators hated dross and buried the same in the shipping bullion, the modern metallurgists from 1925 on decided that with increasing dross-falls they would have to adopt the lead refiner's ideas of drossing kettles with subsequent treatment of the lead with a sulphur addition to have the shipping lead of 0.01

Jan 1, 1950

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By Lo-Ching Chang, J. Chipman

The perennial and increasing interest in the chemical behavior of steelmaking slags has led to numerous attempts to formulate the thermodynamic properties of these solutions. The classical view is that of a solution of the component oxides in which certain acidic oxides are more or less completely held in combination with basic or metallic oxides, the nature of the interoxide compounds being derivable from the chemical behavior of the slag or from the mineralogy of a solidified specimen. The known electrical conductivity of slags has pointed to the existence of ions in the solution and a number of attempts have been made to account for the observed facts of slag behavior on the basis of a theory of complete ionization of the solution. It is the purpose of this paper to examine, in the light of ionic theory, a number of recently published series of data on slag-metal and slag-gas equilibria, with the purpose of obtaining a more complete or more satisfactory generalization than has been possible on either of the single bases of simple compound formation or complete ionization. The attempt to formulate the ionic constitution of a complex solution is fraught with many uncertainties. An ion is not something that can be plucked from the solution and examined in detail, nor can its true formula be determined with certainty by any single experimental method. In attempting to express the composition of a slag by various ionic formulas it can be expected that alternative hypotheses of essentially equal merit will present themselves. In the present state of early development of the ionic theory of slags, it may be necessary to make some rather arbitrary choices of ionic formulas in the absence of su- cient information to yield complete certainty. Acids and Bases The classification of slag-forming oxides as acidic or basic apparently dates back into the days of Berzelius. It is difficult to see how the concept could have originated in the early twentieth century when it was fashionable to define an acid or a base as an aqueous solution containing hydrogen or hy-droxyl ions. It is, however, entirely consistent with the modern and more general theory of acids and bases. In this theory, as originally formulated by G. N. Lewis,' a basic molecule is one that has an electron pair which may enter the valence shell of another atom thus binding the two together by the electron-pair bond. An acid molecule is one which is capable of receiving such an electron pair into the shell of one of its atoms. The acid, the base, and the product of neutralization may be either ions or neutral molecules. The product of such a reaction may itself be a base or an acid if it is further capable of giving or accepting an electron pair. Thus a base is a donor of electrons, an acid, an acceptor. In oxide slags the typical and ever-present base is oxide ion, 0-—. In behavior and in importance it is analogous to hydroxyl ion, OH-, which is the typical base of aqueous solutions. There is nothing in the chemistry of slags which is quite analogous to the acid H30+ in aqueous solutions. This is not surprising for in slag systems there is nothing which can be designated as a solvent and no ubiquitous positive ion. The chemistry of slags is in fact more complex than the chemistry of aqueous solutions and the concepts which must be evoked in its study are correspondingly broader. In seeking a basis for a classification of slag-forming oxides as basic or acidic it must be remembered that these terms are not absolute but relative. A substance which acts as a base toward a second substance may act as an acid toward a third. This is less likely to happen among strong bases or acids than among the weak ones; there are numerous examples of weak acids which under the influence of a stronger acid behave as weak bases. Such substances are called amphoteric. A classification of the glass-forming oxides has been proposed by Sun and Silverman² and further developed by Sun3 in which the oxides are arranged in order of decreasing acidity or increasing basicity, each substance being potentially capable of acting as an acid toward substances below it in the list and as a base toward those above it. It is based upon the relative strengths of the metal-to-oxygen bond as determined by the energy required to dissociate the oxide into its component atoms.' Data are available for computation of this energy, at least approximately, for the oxides of slags and glasses. In general those oxides from which it is most difficult to remove the positive atom are the strong acids while those in which it is most loosely held are the strong bases. It is in the latter, of course, that formation of oxide ion occurs most readily as, for example, in CaO which in solution ionizes to form the weak acid Ca++ and the strong base O—. The order of arrangement found by Sun is shown in the first column of Table 1, to which have been added the data for

Jan 1, 1950

By C. E. Lesher

THIS paper reports a study of the reactivity of 950°F and 1650°F cokes as measured by relative rates of reduction of iron oxides at temperatures up to 2200°F. Previous work cited shows general acceptance of the theory that reduction by carbon is a gaseous reaction, and that kind and character of carbon as well as particle size have measurable effect on the velocity of reaction. As will be shown, the data obtained in this study confirm those conclusions. The work was not designed to examine iron oxide reduction equilibrium, but if reaction velocity be defined as the speed with which "a reaction tends to approach conditions of equilibrium," the data here presented may be considered as a study of reaction rates, and the relative degree of reduction to metallic iron as the measure of reactivity. Three standardized combinations of Lake Superior brown iron ore with carbon were tested by similar procedures. One combination was a mechanical mixture of carefully sized high-temperature coke (1650°F) with the ore. The second was a mechanical mixture of the ore with Disco* obtained by carbonizing the identical coal at 950 °F. The third was an agglomerate prepared by carbonizing the coal and ore at 950°F, premixed in proportions to give as nearly as possible the same relative amounts of carbon and ore as the mechanical mixtures. This agglomerate, obtained by heating the finely divided ore (through 30 mesh) with coking coal through the plastic temperature range so as to form solid aggregates, gives a product in which the oxide particles are impregnated with, and intimately bound together with low-temperature coke. The agglomerate-—ore-Disco—was most active in oxide reduction; the mechanical mixtures of Disco and ore next in order, with coke the least reactive. General Discussion: Carbon exists in many forms and it is well known that the form or nature of the carbon used in reduction of oxides is related to the critical temperature of reduction. Sugar carbon, charcoal, and lampblack are forms of carbon that will reduce oxides at lower temperatures than high-temperature coke, and coke will, in turn, give a lower critical reduction temperature than graphite. There have been many investigations of this characteristic of carbons. Johnson' reported a difference of 130°F (70°C) in the critical reduction temperature of zinc oxide as between charcoal 1891 °F (1033°C) and Acheson graphite turnings 2021°F (1105°C) with zinc oxide. Bodenstein2 using charcoal and coke, found a difference of 138°F (77°C) comparing an experimental figure of 2066°F (1130°C) for coke and 1928°F (1053°C) for charcoal, in the reduction of zinc oxide. He concluded that this is very marked and observed that the "type of carbon merely raises or lowers the temperature at which rapid reaction takes place." Comparing the effectiveness of types of carbon in reduction of zinc oxide, it was found that a "brown coal coke" gave 97 pct zinc elimination at 1832°F (1000°C), as compared with 48 pct with "hard coal coke."' A wide range of metallic oxides was studied by Tammann and Sworykin,4 who found that the temperature at which decomposition of oxides begins depends on the nature of the carbon used. Carbon in the form of graphite, lampblack, and sugar carbon was investigated. Sugar charcoal will reduce Fe2O3 to Fe3O4 at 842°F (450°C) as compared with 1112°F (600°C) for coke, according to Meyer." Direct reduction of iron oxides by charcoal begins at 1382°F (750°C), but "first becomes intense" at 1652°F (900°C), whereas with coke, direct reduction begins at 1742°F (950°C), and "first becomes appreciable" at 2012°F (1100°C).6 he total reduction of the sample under certain conditions when heated in a current of CO with charcoal was about 100 pct for limonite and about 77 pct for magnetite. Using coke under the same conditions, the respective percentages were 75 and 47. In a study of processes for sponge iron7 by the Bureau of Mines, the conclusion was reached that a low-temperature char from noncoking subbituminous coal is the most satisfactory solid reducing agent. In a critical study of zinc smelting from a theoretical viewpoint Maier8 concluded that the reduction is by CO, that the reaction between ZnO and CO is intrinsically more rapid than the subsequent reduction of CO2 by C, which is limited by diffusion rates, which in part effectively limits the smelting process. Maier said that the operation is improved with the activity of the reducing carbon. An active carbon, he said, is one maintaining a low CO, content in the retort. Reactivity of Carbon: One form of carbon is more potent in reducing oxides than another. A carbon that reacts faster than another at a given temperature is said to be more reactive. Reactivity is measured by several methods, using carbon dioxide, air, or steam as reactants.9 ebastian and Mayers" have developed a method for the determination of absolute reaction rates between coke and oxygen by a study of ignition points under certain conditions. These and other investigators have established the relative reactivity of types of carbon. Lignite, charcoal, bituminous coal, cokes in the ascending order

Jan 1, 1951

By David Moskowitz, Ira Binder, Robert Steinitz

THE hard refractory borides of the transition elements of the 4th, 5th, and 6th groups of the Periodic System have been the subject of a number of recent investigations.'-' It is well known now that most of these elements form several different borides, and Kiessling8 has summarized the rules which govern to some extent the arrangements of the boron atoms in the various structures. Melting points of a few borides have been published." The systems Fe-B, Ni-B, and Co-B have been reported," but, as these borides are rather low melting, they are outside of the groups of boron compounds considered here. Brewer' has tested the stability of various borides and estimated a number of eutectic temperatures between different borides, but in no case was the complete system of a transition metal and boron investigated. The phase diagram becomes of special importance if the preparation of the borides from the elements in powdered form is considered; the lowest eutectic temperature will determine the first appearance of a liquid phase. Also, the knowledge of high temperature phases, if they exist, is important for the preparation of bodies from these borides by hot pressing or sintering. During the investigation of various metal borides,7 it was found that there were more boride phases existing in the Mo-B system than reported by Kiessling." They occur, however, only at temperatures above 1500°C and were, therefore, not found by him. This led to a study of the equilibrium diagram of the Mo-B system. ranging from 0 to 25 pct B and from room temperature to the liquidus. Part of this investigation was reported during the "Research in Progress" session at the 1952 Annual Meeting of the AIME.11 Raw Materials and Preparation of the Borides The raw materials used were commercial molybdenum and boron powder, both supplied by the Molybdenum Corp. of America. The molybdenum powder was 99+ pct pure? while the boron powder contained about 83 to 85 pct B. A large percentage of the impurities in this powder was oxygen, with the rest formed by iron, calcium, and unknown substances. The low purity of the boron used was, however, not considered detrimental to the final product, as most of the impurities evaporated at the high temperatures at which the borides were formed. The final product always had a minimum purity of 96 to 98 pct (figured as molybdenum and boron), with carbon, iron, and probably oxygen being the remaining products. Carbon is usually present as graphite. The chemical analyses always confirmed the compositions which corresponded to the crystallographic structures as determined by X-ray diffraction, and the boron content of the finished product agreed closely with that of the starting mixture; no boron was lost during the boride preparation. The chemical analysis methods employed for molybdenum and boron were previously described by Blumenthal.12,13 The powders were mixed by hand in the desired proportions, compressed at room temperature under low pressure, and then heated under hydrogen to about 1500" to 1700°C in a graphite crucible to form the borides. Usually, the three well-known borides Mo,B, MOB, and Mo,B,, which are stable at room temperatures, were prepared in this way, and all other compositions were made by mixing these borides in various ratios or by the addition of molybdenum or boron powders for the very low or very high boron contents. Preparation of two-phase compositions directly from the elemental powders was tried only occasionally to check whether equilibrium could be reached in this way. Experimental Procedures The stable borides were mixed in the desired ratios and heated under hydrogen in graphite crucibles to various temperatures. The well insulated crucibles were heated in a high frequency induction furnace. Special care was taken to obtain exact temperature measurement, which proved much more difficult than originally anticipated. It is believed that individual temperature measurements have an error of less than ±25ºC, while melting or transformation temperatures are accurate within ±50°C. The temperatures were measured with an optical pyrometer which was aimed at the closed end of a graphite tube extending down into the crucible. close to the samples. Attempts to measure directly through the hydrogen exit stack failed. The crucible arrangement is shown in Fig. 1. Heating was done at a slow rate to be sure that the temperature inside the crucible was uniform. The specimens were kept at the final temperature for about 30 min. For the investigation of high temperature phases, some samples were quenched. They were heated, without atmosphere protection, in a very small graphite crucible which could be rapidly removed from the high frequency coil, and dropped into water. These quenched samples were afterwards annealed to establish the equilibrium at lower temperatures. The melting points or the positions of the solidus and liquidus lines were determined by heating the specimens to various temperatures and examining them at room temperature for evidence of a liquid phase. These results were checked later on by thermal arrest curves, especially to determine the exact position of the eutectic temperature line. For this purpose about 200 g of the boride were melted in a graphite crucible, in an arrangement similar to Fig. 1. Slow cooling was assured by very good

Jan 1, 1953

By E. T. Turkdogan, Klaus Schwerdtfeger, P. Grieveson

The rate of growth of "Fe4N" on a iron was measured by nitriding purified iron strips in flowing am -monia -hydrogen gas mixtures at 504" and 554°C. It is shown that a dense nitride layer is formed when a zone -refined iron is used in the experiments. With less pure iron, the nitride layer is found to be porous. Through theoretical treatment, the self-diffusivity of nitrogen is evaluated porn the parabolic rate constant, and found to be essentially independent of nitrogen actirlity, e.g., D* = 3.2 x l0-12 and 7.9x l0-12 sq cm per sec at 504" and 554?C. Some consideration is given to the mechanism of diffusion in the nitride phase. THERE is a great deal of background knowledge on the solubility and diffusivity of nitrogen in iron, and on the thermodynamics and crystallography of several phases in the Fe-N system. Although case-nitrided steels have many applications in practice, no work seems to have been done on the diffusivity of nitrogen in the iron nitride, ?', phase. The only work reported on the related subject of which the authors are aware is an investigation by Prenosil,1 who measured the growth rate of the e phase on iron by nitriding in ammonia-hydrogen gas mixtures. EXPERIMENTS Purified iron plates of approximate dimensions 1 by 0.5 by 0.03 cm were nitrided in flowing mixtures of ammonia and hydrogen, in a vertical furnace fitted with a gas-tight recrystallized alumina tube. After a specified time of reaction, the sample was cooled to room temperature by withdrawal to the water cooled top of the reaction tube. The furnace temperature was controlled electronically in the usual manner within *l°C; the temperature was measured using a calibrated Pt/Pt-10 pct Rh thermocouple. For each experiment the iron strip sample was cleaned with fine emery cloth and degreased with tri-chloroethylene prior to the experiment. The ammonia-hydrogen gas mixtures were prepared from anhydrous ammonia and purified hydrogen using constant pressure-head capillary flowmeters. The gas mixture flowed upward in the furnace with flow rate of 400 cc per min at stp. The composition of the gas mixture was checked by chemical analysis at regular intervals. In most cases, the compositions of the exit gas and metered input gas agreed within about 0.3 pct, indicating that cracking of ammonia did not pose a problem at the temperatures employed. Two series of experiments were carried out using two different types of purified iron samples. In the first series of experiments at 550°C, vacuum carbon deoxidized "Plastiron" was used. The main impurities present in this iron were, in ppm: 4043, 50-Cr, 20-Zr, 40-Mn, 20-P, 20-S, 20-C, 50-0, and 10-N. In these experiments the rate data were obtained by measuring the change in weight of the iron specimen suspended in the hot zone of the furnace by a platinum wire from a silica spring balance. The nitride layer formed in these experiments was found to be porous, particularly near the outer surface. In other experiments, high purity zone-refined iron (prepared in this laboratory) was used. The total impurity content of this iron was 30 ppm of which 20 ppm was Co + Ni, 4 ppm 0, other metallic impurities were less than 1 ppm. The zone-refined iron bar, -2.5 cm diam, was cold rolled to a thickness of about 0.03 cm and the specimens were prepared for the experiment as described earlier. After the nitriding experiment, the sample was copper plated electro-lytically and mounted in plastic for metallographic polishing. After polishing, the thickness of the ?' layer was measured using a metallographic microscope. The nitride layer formed on the zone-refined iron was essentially free of pores. RESULTS The different morphology of the nitride layers grown on "Plastiron" and zone-refined iron is shown in Fig. 1. Both samples were nitrided side by side for 55 hr. The holes in the less pure iron, Fig. l(a), are confined to a region about one half thickness from the outer surface. The dense layer grown on zone-refined iron, Fig. l(b), is thinner than the porous layer on the "Plastiron". The impurities in the iron are believed to be responsible for the formation of a porous nitride layer. The pore formation may be due to the high nitrogen pressures existing within the nitride layer, e.g., the equilibrium nitrogen pressure is 1.2 x l05 atm in the 38.6 pct NH3-61.4 pct H2 and 6.6 x l03 atm at the Fe-Fe4N interface at 554°C and 0.96 atm. It is possible that the oxide inclusions present in the electrolytic iron may facilitate the nuclea-tion of nitrogen gas bubbles within the nitride layer. Support for this reasoning is the fact that pores are only encountered in the outer range of the layer where nitrogen pressures are largest. The photomicrographs in Fig. 2 show the effect of reaction time on the thickness of the dense nitride layer formed on zone-refined iron. These sections are from samples nitrided in a stream of 29 pct NH3-71 pct H2 mixture at 554°C for 22, 70, and 255 hr. In all the sections examined the nitride-iron interface was noted to be rugged. These irregularities are be-

Jan 1, 1970

By C. A. Stickels, C. M. Yen

Secondary recrystallization was investigated in vacuum-melted electrolytic iron to which 70 pm N was vacuum-meltedadded. The secondary texture is "near {554}<225>" for material cold-rolled 75 to 90 pct, the sharpness of the texture increasing with increased rolling reduction and with decreased annealing temperature. At reductions of 95 and 97.5 pct the secondary texture is &apos;"near {322)(296)". Both secondary orientations also exist as major components of the primary re-crystallization texture. Development of a strong "near {554) (225)" secondary texture appears to depend on the evolution of the Primary texture to a transition texture depleted in orientations near the secondary orientation before the onset of secondary growth. A variety of qualitative experinzents have been used to show that nitrogen is important in limiling primary grain growth. The presence of nitrogen does not seem essential for the establishment of a transition texture, but a loss of nitrogen during annealing may facilitate growth of grains in the secondary orientation. Secondary grains we shown to form initially at the specimen surface. This is not thought to indicate that surface energies are important in the growth process. It is proposed that the quasi-two-dimensional character of surface grains permits discontinuous growth parallel to the surface before secondary growth of interior grains is possible. An earlier study of recrystallization textures in 90 pct cold-rolled electrolytic iron showed that secondary recrystallization occurred after annealing for several days at 700C1 This type of secondary recrystallization, which had not been reported previously, results in the formation of a strong texture, best described by the indices "near {554}(225)". The purpose of the present work was to investigate the effect of various processing variables on secondary recrystallization in this material and determine the mechanism of secondary grain growth. LITERATURE REVIEW An understanding of the mechanism of a secondary recrystallization process depends on knowing: 1) how grains in the secondary orientation come to be in the primary recrystallization texture; 2) why normal grain growth does not occur; and 3) what factors determine the strength of the secondary texture. For secondary growth of grains of a particular orientation, a certain minimum fraction of the grains must be in that orientation after primary recrystallization. This requirement is apparently satisfied "naturally" in certain systems, i.e., when the primary texture obtained by rolling and recrystallizing material initially randomly oriented contains a sufficient fraction of primaries in the secondary orientation. However, in other cases, e.g., {110}<001> and {100}<001> secondary growth in silicon iron,2 it is necessary to enhance the fraction of primary grains in the secondary orientation by rolling and recrystallizing textured material. In the present case, the "near {554}<225>" orientation is contained within the spread of orientations found in the primary recrystallization texture of iron or bbc iron-base alloys. In systems where the main driving force for secondary growth is the reduction in total grain boundary energy, secondary growth is observed only when normal grain growth is minimized. Four ways in which normal grain growth can be limited are: 1) Limitation by a strong primary texture. When a very strong primary texture consisting of a single component or twin-related components develop, most primary grains are separated from one another by relatively immobile small-angle grain boundaries. The classic instance of this is secondary growth into the primary cube texture in some fcc metals. 2) Limitation by precipitates. Precipitates present in the proper volume fraction with a suitable dispersion will limit primary grain growth. The role of MnS inclusions in impeding normal grain growth in Si-Fe is well-documented.5 3) Limitation by sheet thickness. Normal grain growth slows drastically when the mean grain diameter is of the same order as the sheet thickness. This effect has been used to obtain secondary recrystallization in thin sheets of high-purity silicon iron.&apos; 4) Limitation by solute impurities. It is well-established that certain impurity elements in solution can have a large effect on grain boundary mobility.&apos; However, there does not seem to be any secondary recrystallization process in which primary grain size stabilization has been shown to be due to the drag exerted on grain boundaries by dissolved impurities. In certain systems, e.g., secondary recrystallization in silver,&apos; the means by which normal grain growth is limited has not been identified, and solute-impurity limitation might be suspected. In order to understand the factors which determine secondary texture strength in three-dimensional growth, it is necessary to examine in more detail the current picture of general secondary recrystallization processes. Following Cahn,9 it is assumed that the primary grains have a range of sizes and that secondary growth of one of the large grains in this distribution is possible when it exceeds a critical size with respect to its neighboring grains. The critical size depends on the ratio ?S/?p, where ?s is some sort of average grain boundary energy between the potential secondary and the primary grains and ?p is some sort of average grain boundary energy between primary grains. For a constant primary grain size, the critical size for secondary growth increases as ?$/?p increases. May and Turnbull5 have incorporated the

Jan 1, 1969

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525&apos;C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine&apos; and LOW.&apos; Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468&apos;C, hold 72

Jan 1, 1969

By J. Nagy, D. W. Mitchell, E. M. Murphy

In 1957 research was initiated in the U.S. Bureau of Mines experimental coal mine near Pittsburgh, Pa., to study factors affecting foam generation and transport, to evaluate the effectiveness of high-expansion foam for controlling mine fires, and to develop techniques for applying the method under U.S. mining conditions. These investigations showed that high-expansion foam containing at least 0.2 oz of water per cu ft of foam is effective in controlling experimental underground fires burning coal, wood, and oil. Sometimes the fire was completely extinguished, but more often, it was brought under sufficient control to permit either a direct attack on the fire with a stream of water or loading of the hot material into cars. A progress report&apos; prepared in July 1958 summarized the initial achievements of the USBM experiments. Since then other phases of the foam-plug method for attacking fires have been studied in the laboratory and in the mine. Previous studies by British engineers&apos; of the foam-plug method for fighting mine fires indicated that high-expansion foam was effective in controlling experimental timber fires in an underground passageway. Their subsequent workx-1 pertained to the practical aspects of fighting large fires within a mining area with a foam-plug. CONTROLLING EXPERIMENTAL FIRES In the USBM tests foam was formed by spraying a dilute solution of a foaming agent on a metal or cotton net of 1/8 to 1/4-in. mesh. Air passing through the continuously wetted net forms bubbles of 1/2 to 11/2-in. diam and produces a honeycomb of foam that fills the passageway. Under the ventilating-air pressure, this light-weight plug moves forward through the passageways, around sharp corners, and over obstacles. as illustrated in Fig. 1. High-expansion foam was transported to a wood fire, an oil fire, and 13 coal fires. Figs. 3 and 4 show a typical coal fire before and after attack with foam. In 12 of the 15 experiments the fire was brought under control when the water content of foam was 0.2 oz or more per cu ft. A fire was considered controlled when the flames were quenched and observers could cross the area without wearing breathing apparatus or protective clothing. In the other three experiments, conducted when the water content was less than 0.2 oz per cu ft of foam, the flames were retarded but the fire was not controlled. Coal fires have been attacked successfully by foam introduced at points varying from 155 to 1010 ft from the fire. The time of burning in coal beds 10 in. thick ranged from 11/2 to 5 hrs or more. Most of the experimental fire beds were 15 ft in length. However, in one experiment a floor fire 25 ft long and 5 ft wide was constructed $5 upwind from another fire 15 ft in length; in another instance, the fire was 100 ft long and 5 ft wide. Foam was applied to the fires for periods ranging from 7 to 36 min. The time required for foam application depends on the extent of the fire, time of burning, water content of foam, foam velocity, and degree of fire control desired. In addition to the coal fires, foam was transported to a fire covering 45 sq ft, produced by 15 gal of oil burning in metal trays on the floor. The foam extinguished the oil fire in about 1 min. In one other test, the burning of 1100 lb of dry sawmill slabs stacked in open cribs 4 ft high and 16 ft long was brought under control by foam in 2 min. Composition of Gases in Return Air: In several of the experiments samples of the return air from fire zones were collected; composition of the atmosphere before, during, and after foam application was then determined. Because of condensation in the relatively cool sampling tube, the amount of water vapor was not determined. Analyses showed that concentration of carbon dioxide and combustible gases increased as the foam began passing over the fire. This resulted from the decrease in the volume of air when foam generation started and from the formation of gases when water reached the fire.* The quantity of gases generated would not be greater than that from an equivalent amount of water applied directly to the fire. The highest total concentration of combustibles (CO, CH1, and H2 mixture) obtained during the experiment was about 2 pct; this occurred 6 min after foam reached the fire. This atmosphere was nonex-plosive, but calculations show that if the air flow were reduced to about 5 fpm and if the rate of gas liberation from the fire remained constant, the mixture would be explosive. The use of foam on a fire in all probability would affect the normal ventilation of a mine. If the mine is gassy, this factor must be carefully considered before the foam is applied. APPLICATION OF THE FOAM-PLUG TECHNIQUE IN MINES Equipment and procedures for applying the foam-plug methods must be adapted to the prevailing conditions at a particular mine. Some factors to be considered in developing equipment are: size or extent of the mine, dimensions and number of entries, ventilation system, mining methods, haulage facilities, availability of water, amount of methane liberated, and existing fire-control apparatus. • In most experiments the initial air velocity of 200 fpm decreased to 50 to 100 fpm as the foam plug increased In length.

Jan 1, 1961

By R. Silverman, H. Blumenthal

It was found that despite the similarity of chemical analyses of different titanium carbides used as base materials for cermets, the physical properties, especially transverse-rupture strengths, of test bars were different. Hence this metallographic study attempts to link physical properties to micro-structures. It is shown that microstructure, grain shape, and grain growth are functions of three interrelated factors: 1—powder production procedure, 2—surface conditioning of the particles, and 3—impurities either contained in the original powder or acquired during ball milling. An explanation is offered for the "coring effect," long observed, but heretofore of unknown origin. The explanation is based on assumption of an oxide film and on chemical analyses which substantiate these findings. TITANIUM carbide has become in recent years a material of great interest in the high temperature field. Consequently, many manufacturers in the United States and Europe are producing titanium carbide for cermet applications as well as for additions to the well known tungsten carbide tools. All present commercial processes of titanium carbide production utilize the chemical reaction of titanium dioxide and carbon to form as nearly as possible stoichiometric Tic. This reaction is carried out in three ways: 1—in a menstruum of molten metal,&apos; 2—in the solid state, either in a protective atmosphere2 or in vacuum;" or 3—in an are-melting operation. In spite of the fact that the pure carbides obtained in these operations are almost identical chemically, the physical properties vary considerably when they are combined with a binder (Ni, Co) to form cermets. This fact led the authors to examine metal-lographically nickel-bonded titanium carbide in order to find the possible reasons for this behavior. Materials and Methods Five different titanium carbides were used in this investigation. They are identified in Table I. The first four materials were used in the as-received condition. Material E, received in lumps, was crushed to —100 mesh and carried through a flotation process in order to bring its graphite content in line with the other products. A Galagher flotation cell was used with pine oil as frothing agent. The chemical analyses of the investigated materials are given in Table 11. The binder used was carbonyl nickel of 9 to 14 microns particle size, supplied by A. D. Mackay. The materials were ball milled at a ball to charge ratio of 6:1 using procedures described under "Experiments and Results." All particle sizes mentioned are averages determined with a Fisher Sub-sieve Sizer. Test bars (lx0.40x0.16 in.) were prepared by 1—hot pressing to 85 to 95 pct of theoretical density at pressures between 1 and 1½ tsi and temperatures from 1600" to 1800°C, 2-—-cold presssing after 3 pct camphor had been added, or 3—wet pressing, both 2 and 3 at pressures between 5 and 10 tsi. All pressed bars were sintered in a vacuum of 105 to 10-6 mm Hg for 2 hr at 1350 °C. Transverse-rupture strengths were determined by breaking on a Baldwin Universal Testing Machine over a 9/16 in. span. Densities were measured by water displacement. The preparation of the specimens for micrographs was done according to Silverman and Doshna Luscz." All magnifications are at X1000. A sodium picrate electrolytic etch was used. Experiments and Results The influence of ball-milling procedure, ball-milling medium, pressing procedure, and sintering procedure on the microstructure of 80/20 — TiC/Ni were investigated. Ball Milling of Materials A, B, and C in a Steel Mill: Figs. 1 and 2 show microstructures of hot-pressed and vacuum-sintered test bars of materials A and B after the respective materials had been ball milled to 2.1 microns particle size in a steel mill and mixed with 20 pct Ni binder. Material A (Fig. 1) shows considerable grain growth. Also evident is a tendency of the carbide grains to coalesce. The density is 98 pct and the low transverse-rupture strength of 111,000 psi is probably caused by many large grains and an unfavorable packing factor. Almost all grains show a slight indication of "coring." Material B (Fig. 2), although showing grain growth, still has many small particles and a better distribution of binder and carbide due to the relative absence of the coalescing tendency. "Coring" can be observed in almost all grains. The high transverse-rupture strength of 179,000 psi and the density of 100 pct are believed to be due to the many small grains completely surrounded by the binder phase. There is also a preference to form spherical grains with material A, while most grains of material B preserve their angular shapes. Material C, of which no picture is given, stays between A and B in every respect. Rounding of some grains can be observed as well as coring, but the latter to a lesser degree than with material B. Its densification is good and the transverse-rupture strength obtained is 142,000 psi. Ball Milling of Materials A, B, C, and E in a WC Mill: When the Tic powders were ball milled to 2 microns particle size in a we mill, then ball-mill mixed with 20 pct Ni binder, hot pressed, and vacuum

Jan 1, 1956

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith&apos; while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith&apos;s experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours&apos; exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960