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ONE DAY IN the mid-1880s, in a suburb 0f Pittsburgh, Pennsylvania, there dismounted from a train the two foremost leaders of the day in the coal and steel industries-Andrew Carnegie and H. C. Frick. Their attention was drawn to a well-loaded car of coke, which their experienced eyes recognized as a superior product. "I'll bet you that coke is from the H. C. Frick Coke Company," Mr. Frick challenged. "I'll bet it was shipped by my company." In a spirit of fun Mr. Carnegie accepted the wager. Mr. Frick lost the bet: the coke had come from M0rewood, one of three sites being operated under the direction of a young entrepreneur, Erskine Ramsay. If Mr. Frick's confidence was somewhat dented by this occurrence, the responsibility was his own. He himself had opened the way for Erskine Ramsay to become the youngest of mine superintendents; and he had dispersed all dissension regarding his choice with the words : "I'm not interested in his years, I'm interested in his record. He makes more coke in an oven than any other superintendent. And I'll take 'em out 0f the cradle if they can make coke... Suppose he is only twenty years old? ... The d --- kid is a genius, I tell you." Erskine Ramsay was to follow in the tradition of Carnegie and Frick. Not only was he ambitious and a worker his background had prepared him for it. Coal mining was in the Ramsay blood. His father, Robert Ramsay, of whom the son once stated that he had no superior as coal mining and mechanical engineer in this country, once accounted in these words for the phenomenal accomplishments which had attached to the name "It does no harm to belong to a family of mining engineers who are just as good as any in America-if it is myself that says it." Anyone acquainted with Robert Ramsay's character realized that he was not given to overstatement. And the above-mentioned Mr. Carnegie encountered young Ramsay again, a few years later in his career, and wrote of him to young Erskine's father, that he was "going to be a credit `tae us a' " (a quotation from Robert Burns.) Nor have Mr. Ramsay's achievements been identified exclusively with the industrial field in which he early asserted himself. He has been an inventor whose techniques in mining engineering have received international recognition. As an investor of foresight, he has benefitted others immeasurably, as well as himself, being an influential factor in the upbuilding of several communities in his chosen and well-loved adopted home state of Alabama since 1887. He is a philanthropist whose benefactions have run into millions, the chief beneficiaries being educational and charitable institutions. Amidst his accomplishments the lighter side of life has not been neglected and he is known for his hospitality, his

Jan 1, 1953

By A. M. Gaudin, J. H. Brown

In a survey of the effects of heat treatment on the comminution of various rocks, it was found that unusual size distributions often characterize the broken products, and that this is related to a great increase in intergranular fracture1. It is the purpose of the present paper to contribute to an understanding of this effect. In a thesis by one of use, critical consideration was given to many mechanisms which could conceivably be responsible for the increased intergran-ular fracture. It was shown that neither gross chemical changes nor intergranular corrosion are required. Among non-chemical mechanisms the most likely appeared to be (1) Uneven expansion due to thermal gradients, giving spalling (2) In a manner similar to that prevailing in metals, the appearance at high temperature of intergranular weakness. (3) Unequal thermal expansion of adjacent grains. Experiments were designed and conducted to permit a choice among the many alternative mechanisms and in particular among the three listed here. EXPERIMENTAL MATERIALS Tests were made on the materials listed in Table 1. Of each material, only lumps similar in composition and grain size were used. The three marbles listed in Table 1 were analyzed to assure that their chemical compositions did not differ greatly (Table 2). On the basis of the chemical analyses, of differential thermal analyses, and of X-ray powder diffraction patterns, it appeared that the marbles were very similar except for their grain sizes.

Jan 1, 1961

By D. Turnbull, H. N. Treaftis

Precipitation of tin from Pb-Sn alloys (lead-rich) occurs by the nucleation and growth of hemispherical cells which consist of tin lomelloe interspersed in the depleted solid solution. Nucleation and growth of these cells and the tin interlamellar spacing at various compositions and temperatures have been investigated. The interlamellar spacing increases approximately as the reciprocal of the logarithm of the supersaturation ratio. For constant initial tin concentration the concentration of cell nuclei increases with decreasing temperature to a limiting temperature-independent value. The kinetic results support the view that the cell growth rote is governed by the diffusion of tin along the cell boundary. In the main, the results confirm the authors' earlier deductions, drawn from resistometric and calorimetric data, about the precipitation mechonism. IT has been shown1, 2 that tin (ß) precipitates from lead-rich (a) PbSn solutions by the nucleation and growth of cells (cellular or discontinuous precipitation). These cells consist of tin lamellae, with a spacing 1, interspersed in a depleted a solution. Reorientation of a also accompanies cell growth. The kinetics of cellular precipitation of tin from lead have been measured by resistometric2, 3 and ca1orimetric1, 3 techniques. The time-transformation isotherms (t equals time; x, volume fraction of specimen transformed) of the initial rapid precipitation, which drains about 60 pet of the tin from solution, have been described by a kinetic law having the form x = 1 —exp (—bt n) [I] where n usually has the value 3.0. It was shown" that this law and the other kinetic facts can be explained satisfactorily if it is assumed that the cells grow at a constant rate and that all the cells nucleate in a time negligible in comparison with the period of cell growth before impingement. Thus, for hemispherical cells b = (2/3)pNG3 [21 where G is the rate of cell growth in cm per sec, and N is the number of cell nuclei per unit volume. The rapid rate of cell growth at low temperatures can be accounted for"' if it is assumed that the dissolved tin drains to the lamellae edges by diffusion along the sweeping cell boundary rather than by diffusion through the a crystal (volume diffusion). For cell growth governed by cell boundary diffusion it was shown, approximately G=2(X° - X° / X° ) DBA / l2 where A equals the thickness of the cell boundary; D R, the coefficient of diffusion of tin atoms within the boundary; and X° and X, are the atom fractions of tin in the supersaturated and saturated solutions, respectively. Zener8 had already shown that, where

Jan 1, 1959

By C. H. Wayman, D. W. Fuerstenau

The effect of bubble size and concentration of certain reagents on the terminal velocity, shape, path, and drag coefficients of single air bubbles in distilled water has been investigated. Bubbles of a certain size range rise considerably faster than Reynolds number-drag coefficient relationships predict, whereas a small amount of frothing agent reduces their terminal velocity. The rapid velocity at which bubbles rise in distilled water appears to result from slip at the boundary and from circulation within the bubbles. Surface-active agents retard bubble motion through prevention of both circulation and slip at the boundary. A surface tension concentration gradient helps maintain bubble sphericity. HE gas phase is one of the indispensible in-gredients in flotation operations. Flotation depends on the collision of an air bubble and a mineral particle in a pulp and their ability to remain in contact long enough for adherence to take place. Before it is possible to understand the mechanics of air bubble-mineral particle encounter, it is necessary to learn more about the nature of bubbles themselves before collision with a mineral particle has taken place. To date, little work has been done on air bubbles in flotation systems. In 1945 Fahren-wald' presented a study of the role of frothers on air bubbles and on aeration in flotation, and recently Wark and Sutherland' discussed the work of Rosenberg- in relation to flotation. The research reported in this present article was undertaken to investigate systematically the effect of bubble size and the concentration of certain reagents on the terminal velocity, shape, path, and drag coefficient of single bubbles in distilled water. Most of the work is concerned with the effect of a-terpineol on bubble motion in water, but studies were made with potassium chloride, potassium hydroxide, potassium ethyl xanthate, and potassium amyl xanthate. Experimental Method and Materials: To obtain free bubble rise and reduce wall and surface effects, the investigators used a tank of 5½x5½x30-in. internal dimensions, filled with water to within 4 % in. of the top.' The tank was made of acrylic plastic so that the walls would have good optical properties. Distilled water, which was re-distilled in a block tin still and saturated with air before each test, was used in all the experiments. All solutions were made with reagent-grade chemicals. During each experiment the water was at room temperature, and during the course of an experiment the temperature did not fluctuate more than 0.5°C. Since the experiments were performed over a period of six months, the temperature varied between 25° and 27°C. The temperature at which each series of experiments was conducted is recorded with the data. The experimental apparatus is presented dia-grammatically in Fig. l. Individual air bubbles were generated from purified compressed air through a capillary of 0.003-cm internal diameter at a rate

Jan 1, 1959

In 1962, minerals beneficiation showed definite signs of coming out of the doldrums into which it has drifted after the uranium boom. Demand by steelmakers for high-grade iron pellets has created the need for concentrating plants to upgrade specular hematite by spiral concentration or flotation and magnetites by magnetic means and flotation. According to a paper given at the AMC annual meeting by C. S. Arms of Pickands Mather, "the shipment of pellets, started in the mid-1950's, has increased to 17.6 million tons in 1961 from North American operations. Many plants already underway will raise this production to about 42 million tons by 1965. This will be a very sizeable percentage of the total iron ore production contemplated by that date." Iron ore concentration methods are gradually raising the assay of pellets into the 65 to 69% Fe range and lowering silica to the 4 to 7% range. Quebec Cartier's Lac Jeannine concentrator went into operation in late 1961 and all grinding units were running by 1962. The Iron Ore Co. of Canada's new Carol Lake plant was started in mid-1962.

Jan 2, 1963

By J. W. MacDonald

Review of equipment, performance, and shaft design plans including head-frames for sinking and forms for lining are given. Also included are comparative data for shafts of 11 x20 ft and 193/4 x 30 ft with 756 and 666-ft depths, respectively. Advantage from curtain wall installation with "slip forms" which warrant consideration for normal lining are outlined. A preliminary review is also made of "chemical grouting" to stop water inflow leakage with Halliburton equipment and service. Two coal mine shafts recently completed in Franklin County, Ill., afford experience and accomplishment to warrant review. These shafts provide access to a tract with a potential recovery of one hundred million tons. This work provided the initial sinking by other than a contractor's organization since 1918. Four additional shafts required during the interim were sunk under contract arrangement with others. Supervisory contact and inspection afforded experience to govern planning and conduct of the recent work. TEST DRILLING Core test holes were drilled within each of the two shaft locations. Four additional cable tool holes were drilled on a radius of 700 ft from the shaft bottom to determine the coal seam elevations and govern the underground layout plans for each shaft. A graphic log of the hoist shaft test drillhole is shown by Fig. 1. A very soft sandstone was found at a depth of 16 ft. Cored recovery of the sandstone proved much weaker than the overlying compacted sand secured with coring facilities for soil recovery. Gradation from the very soft sandstone to fairly hard material occurred with the next 14 ft, extending to a depth of 30 ft. The weak character within the upper portion entailed need of adequate protection when sinking as described later. A part of the sandstone provided sufficient porosity and permeability to warrant further investigation. Adjacent cable tool drilling for temporary water supply disclosed inflow was limited to 2 gpm with a depth of 40 ft. It was increased to 12 gpm during the next 50 ft of drilling and occasioned subsequent precaution when sinking. General arrangement of facilities for sinking the hoist shaft is shown by Fig. 2. An available steel frame building was used to accommodate the hoist, compressor, shop, and shower or change room. The stiff leg derrick with 90-ft length of boom permitted removal of forms from the wood shop to the storage area or delivery within the shaft. Reinforcing steel and other needs were similarly handled, in addition to headframe erection. The headframe was placed over one end of the shaft to enable passage of forms for lining through the adjacent half next to the stiff leg derrick. The steel headframe as shown by Fig. 3 was fabricated locally. Side anchored cables from the

Jan 1, 1961

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By D. J. Mack, R. E. Reiswig

Six examples of the peritectoid transformation were selected from the literature and studied by the method of isothermal transformation. The kinetics and mechanisms of five of the examples are presented as TTT diagrams and photomicrographs. The exist-enc- of a peritectoid in the sixth case is doubtful. ALTHOUGH the peritectoid transformation per se has been known for many years, no precise published data exist concerning the kinetics or mechanisms involved in transformations of this type, except for the brief treatment by Rhines, et al. 1,10 Bearing in mind the fact that investigations of recent years are uncovering more and more peritectoids and suspected peritectoids, a thorough study of the well-established peritectoids appeared to be in order. It was for this reason that a study of the kinetics and morphological mechanisms of six binary peritectoids was undertaken. The six peritectoids selected from the literature for study were those reported at 7.02 wt pct Al-Ag, 26.0 wt pct Sb-Cu, 30.5 wt pct Sb-Cu, 32.3 wt pct Sn-Cu, 8.35 wt pct Si-Cu, and 21.2 wt pct Al-Cu. These selections were based on availability and purity of components, ease of preparation and heat-treatment, and estimated reliability of the available equilibrium diagrams in the regions of interest. EXPERIMENTAL PROCEDURE The alloys used in this investigation were induction melted in electrode-grade graphite and chill-cast in cast-iron split molds. In all cases, the alloys were so brittle that they could easily be broken into samples weighing 1 or 2 g. Chemical analyses showed that the alloys used were close to the respective peritectoid compositions reported in the literature and that the impurity levels were low in all cases. Metallographic examination showed uniform distributions of phases in all samples, indicating uniformity of composition in the samples studied. Isothermal transformation studies were carried out in fused-salt media, using the familiar inter-rupted-quench method. Uniformity of temperature in the salt baths was maintained by continuous stirring with a stainless-steel agitator. On the basis of actual observations of the temperature fluctuations, the estimated temperature control was + 10C for the Ag-Al and Cu-Sb alloys and ±30C for the Cu-Sn, Cu-Si, and Cu-Al alloys. The accuracy of all temperature measurements was estimated to be ±1°C. It was found necessary to mount metallographic specimens of the Ag-Al alloy in cold-curing methyl methacrylate, since the temperatures encountered in mounting in bakelite or lucite caused an appreciable degree of transformation to the ß phase. For the other alloys, wood-flour-filled bakelite mounts were used to avoid extraneous X-ray diffraction lines during the later examination of the metallographic specimens on a Norelco Geiger-counter d if f r ac tomete r. In the X-ray diffraction procedure, agreement between the published diffraction patterns and those obtained in this study was good. This was particularly important for phase identification, since the literature contained little in the way of micrograph description in some cases. Etching of the silver-aluminum alloy for metallographic examination was done by swabbing with either of the following reagents: 1) 10 g CrO3, 1 g (NH4), SO2, 0.5 g NH4NO3, 100 ml H2O, or 2) 10 ml NH4OH, 1 ml 20 pct KOH, 4 ml 3 pct H2O2, 5 ml H2O. The other alloys were etched with the usual bichromate etchant: 2 g K2Cr2O7, 1.5 g NaC1, 8 ml conc. H2SO4, 100 ml H20 (swabbed vigorously). EXPERIMENTAL RESULTS A) The Ag-Al peritectoid at 7.02 wt pct Al— The phase equilibrium involved in this peritectoid is shown in Fig. I.2 The phase boundaries in the vicinity of the peritectoid were most comprehensively established by Hume-Rothery, et al,3 who placed the equilibrium temperature at 448 °C and the equilibrium compositions of the a ß&apos; and y phases at 6.11, 7.02, and 7.24 wt pct Al, respective The alloy used in this study analyzed4 6.95 wt pct A making it slightly hypoperitectoid according to the accepted equilibrium diagram. The rate of the transformation a+ y — ß&apos; varies rapidly with degree of undercooling below the equilibrium temperature, passing through a maximum in the vicinity of 350°C. Thus the TTT dia-

Jan 1, 1960

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO&apos;3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.&apos; In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those&apos;used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By J. M. Woodall

GuAs crystals which have been grown in quartz boats by the horizontal Bridgman method in the pvesence of Ga20 vapov have beetz found to have carrier and donor distributions which do not correspound to those expected from simple dopant seg-vegation during directional freezing; Instead, the carrier distribution is determined by the heat-trentnzent history of the crystal, while the donor distribution, zohiclz is principally due to silicon, is fixed by the pozuth rate, the geo)tlet.ry of the crystal growth vessel, and tlze initial Ga20 pressure. WHEN semiconducting materials are made into doped crystals by the normal freezing method,&apos; they usually exhibit doping variations along the growth axis. If a) there is no dopant diffusion in the solid, b) the dopant is distributed uniformly in the melt, and c) the distribution coefficient, k, does not vary with composition, then the doping variation along the growth axis is represented by the equation: where C is the doping level in the solid at a point where a fraction g of the original liquid has frozen, and Co is the mean concentration. When the dopant is either a singly ionized shallow donor or shallow acceptor, C also represents the carrier concentration. Even though this equation accurately describes the dcping profiles of a large number of normal freeze systems, there are several special systems for which Eq. [I] does not apply. One such system is the horizontal Bridgman method for preparing oxygen-grown GaAs crystals using quartz vessels. Several workers2"* have shown that GaAs crystals grown by the horizontal Bridglnan method using quartz vessels are generally contaminated with silicon in concentrations in excess of 5 < 10lG atoms per cu cm. This contamination is ascribed to a reaction: occurring at the walls of the crystal-growth vessel which liberates silicon into the melt and Ga2O vapor. It has been shown4 that this reaction, and, hence, the silicon contamination, can be suppressed by the addition of oxygen to the crystal-growth apparatus. It is the purpose of this paper to describe a special apparatus capable of yielding single crystals of GaAs grown in the presence of oxygen and to describe both the kinetics of silicon suppression in this system and the relationship between the carrier concentration profile and the silicon concentration profile. EXPERIMENTAL-CRYSTAL GROWTH A schematic diagram of the apparatus used in the oxygen addition experiments is shown in Fig. 1. The most important features of this apparatus are: a) the use of a sand blasted quartz boat, h) a quartz rod of length 1, with a hole of cross section A, that is placed near the boat to limit the free space volume V, over the melt during the growth, and c) the temperature gradient at and near the solid-liquid interface. Sand blasting the boat is necessary to prevent wetting of the melt. The quartz rod retards the diffusion of the GazO vapor away from the melt to the colder portions of the ampoule. A crystal is prepared by first loading a 5.5-in. boat, which has been cleaned in aqua regia, with 40 g of 99.9999 pct Ga along with 1 to 8 mg of Ga203 powder. GazO3 is a convenient source of oxygen since it reacts with gallium at the melt temperature to form Ga20 vapor, the species which apparently controls the suppression of silicon contamination. The loaded boat, the quartz rod, and the 99.9999 pct As are placed in the ampoule as shown in Fig. 1. Generally, GaAs seeds were not used since most of the unseeded growths resulted in monocrys-tals. The ampoule is evacuated to 10-5 Torr and sealed off. The GaAs melt is synthesized by placing the ampoule into a two-zone horizontal Bridgman furnace. The two zones are separated by several sandwiched layers of -in. Fibre-Fax board drilled with holes slightly larger than the OD of the ampoule. This causes a very large temperature gradient between the two zones, which is necessary for single-crystal growth. The two-zone furnace is mounted on a stand fitted with a roller bearing which allows uniform motion of the furnace in a horizontal direction. A uniform velocity of the stand is achieved by the use of a windlass device which winds up a wire attached to the stand. Movement of the solid-liquid interface is accomplished by fixing the position of the ampoule and moving the stand. Growth rates investigated in this experiment were between 0.4 and 1.2 in. per hr. The composition of the melt is fixed by maintaining an arsenic reservoir at 618°C. The stand is moved away

Jan 1, 1968

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram&apos; shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole&apos;&apos;) and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-&apos;) is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-&apos; using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- &apos; torr, Maiya and lakel measured y as 39 kcal mole-&apos; using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-&apos;: there is evidence also for a low temperature value of about 20 kcal mole-&apos;. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.&apos;-&apos;&apos; Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A&apos;, C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2&apos;3 M = mass of an evaporating molecule

Jan 1, 1970

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.&apos; In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim&apos;cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors&apos; knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad&apos;s analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier&apos;s conclusion.

Jan 1, 1964

By R. L. Fleischer, W. F. Hosford

Tensile data for coarse grained aluminum Polycrystals suggest that the "grain size" effect is not due to dislocations piled up at grain boundaries but rather is primarily a relative size effect due to surface crystals being weaker and less confined. STUDIES directed at interpreting hardening of poly-crystalline metals normally identify their strain hardening properties with those in some particular type of single crystal.1"4 The recent recognition in face centered-cubic metals of a nearly linear stage with rapid hardening occuring at comparable rates for both polycrystals and single crystals, suggested that the same process or processes determine both cases and hence that there exists some justification for the use of single crystals to understand polycrystals. Further evidence for the above view may be found by an approach initiated by Chalmers:5 By using bicrystals of controlled orientation it is possible to begin to assemble a polycrystal and also to study grain boundary effects in detail. In this way it has been found that a single grain boundary affects easy glide but not the subsequent stage II hardening.6 This result suggests that a sensitive way to observe grain boundary effects in polycrystals would be to vary grain size and measure easy glide. As will be seen, easy glide is only possible for coarse-grained samples, and hence the results will serve to fill in the gap in measurements between single crystals and bicrystals on one hand and fine-grained polycrystals on the other. One problem inherent in comparing single crystals with polycrystals is the uncertainty as to what slip systems are acting in a polycrystal. To compare the two types of samples, rates of shear hardeninn---L. on the acting -planes are needed. and these may be computed only if it is known what particular systems are active. The acting systems were examined for a coarse-grained polycrystal and it will be shown that the systems supplying the preponderance of slip can be determined with little ambiguity. EXPERIMENTAL PROCEDURE Twelve samples of aluminum were prepared by chill casting into a heated graphite mold, followed by annealing at 635° ± 5°C for 24 hr with an 8-hr fur- nace cool, and finally either etching7 or electropol-ishing.&apos; The samples, with a 7 to 10 cm length between grips and 4.4 by 6.6 mm in cross section, were deformed at a strain rate of about 3 10 -3 . per min in a tensile device which has been described elsewhere.5 The composition was reported by Alcoa as 99.992 pct Al, 0.004 pct Zn, 0.002 pct Cu, 0.001 pct Fe, and 0.001 pct Si; nine samples were deformed while immersed in liquid helium and three in air at room temperature. The stress-strain curve for one of the samples (P-1) deformed at 4.2 "K has been reported previ~usl~.~ This sample was selected for determination of active slip systems. Eighteen of the crystals were examined by optical microscopy to determine the angles of slip line traces and by X-ray back reflection to determine orientation. By this means the slip planes were determined and the resolved shear stress factors for possible slip systems could be computed. Finally each sample was sectioned so that after etching, the number of crystals could be counted for each of ten newly exposed surfaces. The average of these ten values will be termed n, the number of crystals per cross section. Values of 11, varied from 1.9 (nearly bamboo structure) to 12.7. Sketches of typical cross sections appear in Fig. 1. RESULTS AND DISCUSSION: SLIP SYSTEMS 1) Determination of Acting Slip Planes—The stress axis orientation and operative slip planes in eighteen crystals of sample P-1, as determined by slip line traces and crystal orientation, are summarized in Fig. 2. For one of the crystals two planes had a common trace. so that the traces alone did not distinguish which plane or planes were slipping. However it was found that the stress resolving factor for the primary system was 0.386, .while that for the most stressed system in the other plane (indicated bv the dotted arrow) is 0.138. It will be assumed tgerefore that only the primary plane acted. Since the orientations were determined after extending the samples 4 pct, the stress axes may be rotated from their original value by as much as 2 deg in some cases. It is interesting to note that in five crystals only one slip plane acted, in eight two acted, and in five three planes were observed—an average of two slip

Jan 1, 1962

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins&apos; and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer&apos; type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By F. C. Bond

SIZE of grinding media is one of the principal factors affecting efficiency and capacity of tumbling-type grinding mills. It is best determined for any particular installation by lengthy plant tests with carefully kept records. However, a method of calculating the proper sizes, based on correct theoretical principles and tested by experience, can be very helpful, both for new installations and for guiding existing operations. As a general principle, the proper size of the make-up grinding balls added to an operating mill is the size that will just break the largest feed particles. If the balls are too large the number of breaking contacts will be reduced and grinding capacity will suffer. Moreover, the amount of extreme fines produced by each contact will be increased, and size distribution of the ground product may be adversely affected. If the balls added are too small, grinding efficiency is decreased by wasted contacts that are too weak to break the particles nipped; these largest particles are gradually worn down in the mill by the progressive breakage of corners and edges. Ball rationing is the regular addition of make-up balls of more than one size. The largest balls added are aimed at the largest and hardest particles. However, the contacts are governed entirely by chance, and the probability of inefficient contacts of large balls with small particles, and of small balls with large particles, is as great as the desired contact of large balls with large particles. Ball rationing should be considered an adjunct or secondary modification of the principle of selecting the make-up ball size to break the largest particle present. Empirical Equation In 19521,2 the author presented the following emerical equation for the make-up ball size: B - ball, rod, or pebble diameter in inches. F = size in microns 80 pct of new feed passes. Wi - work index at the feed size F. Cs - percentage of mill critical speed. S — specific gravity of material being ground. D == mill diameter in feet inside liners. K - 200 for balls, 300 for rods, 100 for silica pebbles. Eq. 1 was derived by selecting the factors that apparently should influence make-up ball size selection and by considering plant experience with each factor. Even though Eq. 1 is completely empirical, it has been generally successful in selecting the proper size of make-up balls for specific operations. But an equation based on theoretical considerations should be used with more confidence and have wider application. The theoretical influence of each of the governing factors listed under Eq. 1 was accordingly considered in detail, as described below, and a theoretical equation for make-up ball sizes was derived. Derivation of Theoretical Equation Ball Size and Feed Size: The basis of this analysis is that the largest ball in a mill should be just sufficient to break the largest feed particle into several pieces, excluding occasional pieces of tramp oversize. In this article the size F which 80 pct passes is considered the criterion of the effective maximum particle feed size. The smallest dimension of the largest particles present controls their breaking strength. This dimension is approximately equal to F. As a starting point for the analysis it is assumed that a 1-in. steel ball will effectively grind material with 80 pct passing 1 mm, or with F- 1000µ or about 16 mesh. The breaking force exerted by a ball varies with its weight, or as the cube of its diameter R. The force in pounds per square inch required to break a particle varies as its cross-sectional area, or as its diameter squared. It follows that when a 1-in. ball breaks a 1-mm particle, a 2-in. ball will break a 4-mm particle, and a 3-in. ball a 9-mm particle. This is in accordance with practical experience, as well as being theoretically correct. Confirmation of this reasoning is supplied by the Third Theory of Comminution," which states that the work necessary to break a particle of diameter F varies as F. Since work equals force times distance, and the distance of deformation before breaka4e varies as F it follolvs that the breaking force should vary as F½ These relationships are expressed in Table I, with a 1-in. ball representing one unit of force and breaking a 1-mm particle. This establishes theoretically the general rule used in Eq. 1 that the ball size should vary as the square root of the particle size to be broken. Ball Size and Work Index: The work input W required per ton" varies as the work index Wi, and the

Jan 1, 1959

By Richard L. Ashbrook, John F. Wallace

Several high-temperature eutectics of cobalt and nickel alloys were modified by small additions of selected elements. Thes-e alloys were compared to unmodified melts for microstructural variations. A few modified compositions were selected on the basis of structure and their tensile and stress-rupture behavior determined. The results of stress-rupture tests in air at 1800 F and room-temperature tensile tests of four high-temperature eutectics showed modification capable of producing substantial improvements in properties. The microstructures were altered and mechanical properties improved by: a.) dispersing a subordinate phase more uniformly throughout the matrix; b) replacing large continuous -network or platelike constituents with small equiaxed discontinuous phases; and c) by forming new, finely divided phases. tHE term "modification" is most commonly used to describe the refinement in microstructure of the Al-Si eutectic that occurs as a result of rapid cooling from the melt or on slow cooling after treatment with small amounts of sodium.1 "Modification" has also been used to describe the change from flake to spheroidal graphite in the austenite-graphite eutectic of cast iron.2 This change of graphite shape is accomplished by small additions of cerium or magnesium.3 Other systems have also been shown to be capable of modification, for example: Pb-Sn by copper;4 Al-Cu by sodium;5 Al-Mn by sodium;5 and Pb-Sb by aluminum.5 Although modification of Al-Si alloys and cast irons is usually accompanied by improved mechanical properties, a general definition of modification has been suggested to include the effect of small quantities of impurity elements on the microstructures of all eutectic alloys, regardless of the effect on the mechanical properties.6 In this paper, the term "modification" is employed in a broad sense to include the formation of third phases or even the supplanting of one of the binary eutectic phases by a third phase. The mechanism of modification, as for any solidification phenomenon, must be considered primarily in terms of nucleation and growth. Although both nuclea-tion and growth mechanisms are required to explain all the phenomena observed in connection with the solidification of modified eutectics, various investigators have usually favored one or the other.7"16 It has been shown that modification of a binary eutectic can be effected by addition of a solute element that has greatly different distribution coefficients or k values in the two phases of the eutectic. Under these conditions, differences in the temperatures at the solid-liquid interfaces of the two phases retard the growth of one phase with respect to the other.4 It has also been shown that increased undercooling favors a transition from a rodlike eutectic to a globular eutectic.17 A mechanism proposed for the transition from lamellar to rodlike eutectics depends on the concept of constitutional super cooling.18 The modification of eutectic alloys may be of interest for high-temperature service as well as at room temperature. Although "high-temperature eutectic alloys" may appear to be a contradiction in terms, many eutectic systems, including those studied in this work, have melting points in excess of 2400°F. One of the mechanisms by which high-temperature alloys are strengthened is dispersion of a relatively brittle phase such as an oxide, carbide, or an inter-metallic compound throughout a ductile matrix. For a given volume fraction of dispersed phase, strength is increased by decreasing the size and spacing of the dispersed particles.19&apos;20 Furthermore, room-temperature ductility may also be increased by changing the shape of a brittle dispersed phase from platelike to equiaxed or spheroidal.8 Overaging and redissolving of the secondary phase limit the maximum temperature to which precipitation-hardened alloys can be used. However, in a binary eutectic system, both phases coexist up to the melting point. Although all eutectic structures are not completely stable,21 a dispersion-hardened cast high-temperature alloy might result if a fine distribution of one of the eutectic phases could be obtained during solidification. An additional reason for interest in eutectic alloys is their excellent castability.22 Since eutectic alloys, like pure metals, freeze at a single temperature rather than over a range of temperatures, their castability is superior to solid-solution alloys with long liquidus to solidus ranges. The purpose of this research was to study the effects of small solute additions on the microstructure and mechanical properties of a number of high-melting-point eutectic compositions.

Jan 1, 1967

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.&apos; The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7&apos;8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.&apos;l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969