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By H. M. Katz, J. L. Speirs, F. B. Hill

Jan 1, 1961

By C. G. Dunn, J. L. Walter

The c/laracterzstics of cube-oriented nuclei ard other matrix grains that are associated with secondary, recrystallization to the cube texture in high-purity silicon iron were investigated by me-tallographic and X-ray methods. The results show that the structure consists of relatively perfect grains of average diameter between one and two times the sheet thickness ad that the texture has a moderately strong (110) [001] component and a weak (100) [001] component. The results also indicate that matrix stability results from the two-dimensional nuture of the graitzs and that cube-orzented nuclei are neither more Perfect nor larger grains than other matrix grains but have a preferred [001] direction in the rolling direction and have a more effective driving force for growth than other grains because of a low (100) surface energy. THE structures and textures of fine-grained rnatrices determine to a large extent the kinds of secondary recrystallization textures that form on annealing. The understanding of secondary recrystallization processes therefore depends on adequate information about the initial matrices. Matrices usually have three characteristics: 1) they consist of fine-grained primary recrystallization structures, 2) the fine-grained structures are stable toward normal grain growth, and 3) they contain secondary recrystallization nuclei. Stability toward normal grain growth may be due to either a strong single orientation texture (texture inhibition)' or a dispersed second phase (dispersed phase inhibition).2"4 If normal grain growth is not inhibited by either of these two factors, it nevertheless stops when the average grain size is between one and two times the sheet thick- ness.5 This thickness effect satisfies one of the characteristics of a matrix for secondary recrystallization. Its importance in the development of the cube texture in high-purity silicon iron by secondary recrystallization was pointed out by the authors in a recent paper on tertiary recrystallization7 and will be discussed further in the present paper. Assmus, Detert, and he8 have provided some information on a matrix for secondary recrystallization to the cube texture in silicon iron. They found a (110)[001] or Goss texture with enough spread about the rolling direction to include a small amount of the (100)[00l] orientation. The distribution of the [00l] directions was strongest parallel to the rolling direction for both (100) primaries and cube secondaries. These authors found no correlation between size of a matrix grain and orientation and concluded that some property other than size must be the distinguishing characteristic of the cube-oriented nucleus. No consideration was given, it

Jan 1, 1961

By J. B. Coher, M. B. Bever

COLD work destroys long-range order, as was first observed by Dehlinger and Graf.1 Dahl2 showed that the mechanical disordering caused by cold work produces changes in those properties that are affected by long-range order. The existence of order has a marked effect on tile manner in which an alloy deforms and therefore on its mechanical properties.L' The relation between order and deformation behavior however, is only beginning to be understood. Seemann and G1ander4 suggested that cold work reduces an ordered alloy to a kind of gruel of antiphase domains. According to Cottrell,5 superdis-locations and pairs of dislocations in a slip plane connected by a strip of anti-phase domain boundary provide deformation mechanisms which do not change the state of order. In general, however, slip may be expected to produce new domain boundaries and destroy order if dislocations move on intersecting planes or cut through existing domain boundaries. The yield strength of an ordered alloy may pass through a maximum with decreasing domain size.5"7 The reduction of domain size resulting from cold work may, therefore, lead to a maximum in strength properties. Flinn8 suggests that dislocations can climb by short-range diffusion during deformation and thus can generate domain boundaries not only on slip planes, but also on other planes which will be those with the lowest domain-boundary energy. It has long been known that the rate of strain hardening of an alloy in the ordered state is larger than in the disordered state.3'9 Also the slip bands in ordered CU3, AU10 and Ni3Mn" are finer than in the disordered alloys. The stress which causes initial yielding in Cu,Au passes through a maximum with decreasing domain size.6'12 A maximum has also been observed in the hardness of ordered Ni3Mn as a function of strain.' These observations suggest, but do not prove, that domain size reduction occurs during deformation. According to Fisher13 slip destroys short-range order and thus the strength of an alloy is related to the degree of short-range order present. Rudman and Averbach14 and Averbach et a1.,15 demonstrated that cold work reduces short-range order in copper-gold and gold-silver alloys. Destruction of long-range and short-range order by cold work implies slip on an appreciable fraction of planes. Yielding of an alloy in which short-range order exists or antiphase domain boundaries are present should be discontinuous because the first dislocations moving across the slip plane meet with the largest resistance.5 Such discontinuous yielding has been observed in CU3AU6,16 and Cuzn.l7 This phenomenon, however, can also be explained by mechanisms not involving order.b The published investigations of the effects of cold work on alloys with long-range or short-range order have not been covered thoroughly in reviews of order-disorder phenomena. These investigations, therefore, will be listed here. They have been concerned with strength properties> 2,3,6,8,9,12,16-21 electrical resistivity,2,4,18,19,21-26: thermoelectric power, magnetic properties,2,18,21,26 and X-ray strain'1,2,14,15,27,28 The slip systems and the appearance of the microstructure after deformation in ordered and disordered alloys have also been investigated. 6.10.ll,l7,23,29,30 The alloys used in these investigations were copper-gold. 1-4,6,9,10,14,16,18 23-26,28,29 copper-zinc. L7. 19. 20,30 nickel-manganese,2 11,21 iron-aluminum. iron-nickel,' copper palladium,4,18,22 gold-silver.4,18,22 and palladium-silver-copper.4 In the work reported here. the changes in properties of polycrystalline Cu3Au were investigated as functions of strain in wire drawing and rolling. Specimens were heat treated before deformation

Jan 1, 1961

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' 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' 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 M. O. Holowaty, C. M. Squarcy

Bituminous coal furnaces give way to coke, and by 1880, the American iron and steel industry was growing at a tremendous rate. In the twentieth century, the number of operating blast furnaces was cut in half while pig iron capacity more than doubled. Bituminous coal furnaces Attempts to relieve the shortage of charcoal by the use of bituminous coal in American furnaces began quite early. Use of bituminous coal in the blast furnace was restricted to areas lacking anthracite deposits but rich in deposits of bituminous coaL The largest concentration of bituminous coal furnaces was in Western Pennsylvania, West Virginia and Western New York state. Other areas included Kentucky and southern portions of the states of Indiana and Illinois. The first trials were made in Pennsylvania around 1780. Gradually several more furnaces began charging coal with their burdens as a partial substitution for charcoal. These so called cheaters were numerous, especially in Western Pennsylvania, which around 1810 began to expand its ironmaking capacity to catch up with the Lehigh Valley and the Schuylkill According to the existing references, complete bituminous coal burdens began to be used in this area only around 1840 when the ironmakers hastily adopted the hot blast apparatus introduced from England. The majority of these furnaces were built, however, after 1844 when an extensive experimental program, carried out at the Shenango Steam and Water Hot Blast Charcoal, Coke and Raw-Coal Furnace produced favorable results, with coal containing up to 35 pct volatile matter. The furnace was located near the Shenango River on the Lackawannok Run, five miles northwest of Mercer, Pennsylvania. It was built, owned, and operated by David Hogeland of Mercer. The first furnace was built in 1836 or 1837 as a charcoal furnace. Soon, however,

Jan 1, 1961

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.' To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall' determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot' to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.' Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer' have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By T. J. Whalen, M. Humenik

The liquid surface tension of copper-nickel ad copper-nickel-titanium-carbon alloys and the wettability of titanium caybyde by these alloys have been measuhed. It was found that the surface tensions of the binary copper-nickel alloys Lie on a smooth curve between the end members, copper and nickel. The addition of small amounts of titanium and carbon has nO effect on the surface tensions of copper-nickel alloys. Small additions of nickel to copper significantly reduce the contact angle of Ike alloy with titanium carbide. From a Gibbs treatment, nickel is shown to be adsorbed at the titanium carbide-alloy interface. X HE microstructure of two-phase materials has been shown to be influenced largely by the interfacial energies between the phases present.' , In systems prepared by powder metallurgy techniques and densi-fied in the presence of liquid phase, a precise analysis of microstructure and interfacial energy relationships requires a knowledge of the solid-solid interface energies and liquid-solid interface energies. However, marly metal-nonmetal systems are characterized by the "sweating" of the liquid during sintering, and in these systems wettability is a principal consideration. The wetting in turn is dictated by the various interface energies of the system, as shown in Fig. 1 for a liquid drop formed on a solid substrate. The equation which expresses the vectorial balance of surface forces in the horizontal plane, at the point of contact, A, is given by: where ssv = solid-vapor interface energy sSL = solid-liquid interface energy sLV= liquid-vapor interface energy 6 = contact angle measured through the liquid phase. The angle and the surface tension, slv, can be measured accurately by the sessile drop method.3, The absolute value of the surface energy of the solid cannot be determined by this method, but with reasonable changes in the composition of the liquid only, the value of ssv can be considered constant. The changes in contact angle, then, can be attributed to changes in sSL and sLV and since sLV can be measured, the changes in sSL can be determined. Several studies have indicated that the surface and bulk properties of solid alloys can be correlated with electronic structure. The catalytic activity of copper-nickel alloys was reported to follow the dband vacancies in these alloys.5 Nickel has been considered to have 0.6 holes per atom in the d-band. The addition of copper to nickel is thought to bring about a filling of the d-band of nickel, since each copper atom contributes one electron. Thus, at an atomic concentration of 60 Cu-40 Ni (62 wt pct Cu-38 wt pct Ni) the d-band is believed to be full, and magnetic measurements support this view.6 If the electronic structure is influencing a property of the alloy, this property should show some sort of discontinuity as the composition changes from one side of the 60 Cu-40 Ni composition to the other. Since the catalytic activity can be considered as a surface property of the alloy, it is logical to assume that other surface properties, such as surface tension, may also be influenced by electronic structure. The suggestion has been made that there is a correlation between the solid titanium carbide-liquid Cu-Ni alloy interfacial energy and d-band filling.7 One purpose of this investigation was to determine if the changes taking place in the electronic structure with compositional changes in the solid copper-nickel alloys were reflected in the surface tension values of the liquid alloys. Such a change, if present, would lend support to the suggestion that one can refer to discrete energy bands in the liquid state. Other purposes of the present study were to investigate in detail the wettability in the system copper-nickel-titanium carbide, and to discuss the possible processes which take place during wetting in this system.

Jan 1, 1961

By E. J. Roberts

Hydrometallurgical operations and many processes in the chemical industry require the separation of dissolved material from solids. One of the decisions which has to be made in designing a plant for such an operation is how this separation shall be accomplished. It is the purpose of this paper to set forth the general principles involved in such separations in order that the optimum flowsheet and equipment may be selected. Countercurrent Decantation with thickeners, or C.C.D. as it is generally known, is, of course, only one way of separating dissolved material from undis-solved. Other unit operations such as Countercurrent Filtration (C.C.F.) and Countercurrent Classification (C.C.C.) are widely used. The same principles may also be applied to centrifugally assisted decantation, as with nozzle or solid bowl type centrifugals, and to separations using screens, either gravity or centrifugal type. Another form of countercurrent washing applicable to granular materials is practiced in continuous ion exchange operations. All of these operations depend on two basic principles, or combinations of these principles. In C.C.D. type operations the solids are concentrated into the smallest possible volume of liquor in each step and the resulting pulp then mixed with a more dilute liquor and recon cen trated, the liquors separated from the more dilute stages being advanced to dilute the more concentrated liquor in a previous solids concentrate, as is shown in Fig. I. This will be termed the solids concentration-solution dilution principle, or, for short, solution dilution. countercurrent decantation- type circuits. The second principle used in washing solubles from solids is that of solids concentration-solution displacement. Here the solids are restrained from movement while wash solution is forced through the interstices in a counter-current fashion, as in Fig. 2. In the simplest application of this principle, once the "cake" has been formed, it is not disturbed until the operation is completed. In continuous filters, the cake is merely moved under the successive washes and the displaced filtrates removed as in Fig. 4. Often, however, after one or two displacement washes, a repulping step is introduced, the cake reformed and washed again. This procedure brings the solution dilution principle into play as well as the solution displacement principle. Merely thickening ahead of filtration, which is often operationally advantageous, does not hybridize he circuit. It still can be a pure solution displacement operation from the washing

Jan 1, 1961

By W. J. Skewes, C. T. Holland

Properly constructed stopes are necessary underground for proper ventilation and safe, healthful working conditions. Mining companies are concerned with providing the best possible stoppings at an economic cost. It is important to consider 1) proper materials, 2) construction that ensures maximum performance from the material used, and 3) keeping costs within reasonable limits for the unit operation—stopping—involved. The authors investigated all aspects of the problem and have attempted to layout a study program to provide information on all phases. Mining companies every year purchase huge amounts of material for the construction of ventilation stoppings. This material by the time it is in place in the stoppings will cost the company many thousands of dollars. In addition and more importantly these stoppings are supposed to confine air travel along certain well defined paths into areas where it is needed to provide safe and healthful atmospheres for workmen. The cost of forcing this air through the mine is large and in general increases as the total quantity increases. Consequently, if the stoppings leak, increased cost results and in addition unsatisfactory ventilation may prevail in the mine. Therefore, it is essentia1 to provide the best possible stoppings at an economic cost. When attempting to provide the best stoppings possible at an economic cost, three aspects of the problem must be considered. These are 1) getting the most suitable material for stopping constructions, 2) constructing the stopping so as to get the best performance from the material used, and 3) keeping the cost of stopping construction to a minimum for a suitable stopping. This investigation is concerned with all phases of the problem and has attempted to lay out a study to provide information on all of them. In order to develop information on the best stopping material available it seemed wise, after con- sidering the job a stopping must do, to investigate the following aspects of material used for stoppings: 1) strength in compression, 2) compressibility or yield under load, 3) porosity, and 4) permeability. To provide information on the best manner of construction the following aspects of air leakage through the stopping were investigated: 1) when the stopping is built of dry stacked materials—i.e., the joints are not mortar-laid (See Fig. 1); 2) when the stopping is built of dry stacked material and then plastered on one side (see Fig. 2); 3) when the

Jan 1, 1961

By M. V. Nevitt

In the systems Ti-Mn-O, Ti-Fe-O, Ti-Co-O, and Ti-Ni-O the bounda.r-ies of the Ti2Ni-type phases were determined at one or more temperatures and the variation of the lattice parameter with oxygen content was determined. Densities were calculated from the lattice parameters and compared with measured density values. The: results indicate that the occurrence of the phase in these systesms can be correlated qualitatively with valency electron concentration, and that the role of oxygen is that of an electron acceptor. The lower limit of oxygen solubility appears to be determined by the valencies of Mn, Fe, Co, and Ni, while the maximum oxygen concentration coincides with the filling of the 16 (c) positions of the O 7h - Fd 3m space group. THE suggestion has been made by several investigators'" that the phases having the cubic E9,-type structure, and known as 17-carbide-type, double-carbide-type and Ti,Ni-type, are members of a family of electron compounds. This concept has been given additional support by recent work8 in which new isostructural phases involving second and third long period combinations were found, and which provided further evidence of the regularity of occurrence of the phase in terms of periodic table relationships. In this laboratory attention has been focused on the isomorphs containing titanium, zirconium, or hafnium, and the role that oxygen plays in their occurrence. In some binary systems Ti,Nitype* phases occur having the formula A,B where A is the titanium group element. Based on previous workq and the present investigation, oxygen is known to be soluble in two of these binary phases, Ti,Co and Ti2Ni. It is probable that oxygen is also soluble in the other phases of this kind. In other binary systems the Ti,Ni-type phase does not occur, but does occur in the corresponding ternary systems with oxygen .3-5 The experiments described here were performed to determine whether the occurrence and composition of certain of the Ti,Ni-type phases could be related to an electronic effect and whether oxygen's stabilizing role is exerted through an influence on the electron: atom ratio. The ternary systems Ti-Mn-O, Ti-Fe-O, n-Co-O, and Ti-Ni-O were selected for study for two reasons: First, several schemes have been proposed for first long period elements which, although not in quantitative agreement, show a generally consistent trend for the variation of valency with atomic number. Although for a transition metal the term valency is difficult to define and is generally not a constant number which can be applied to all alloys, it is usually assumed to be an index of the number of electrons per atom involved in metallic cohesion. Second, the determination of the Ti2Ni-type phase boundaries was facilitated by the fact that the phase relations in several of these ternary systems have been investigated by other workers."' EXPERIMENTAL PROCEDURE___________________ The alloys were prepared by arc melting crystal-bar titanium, reagent grade TiO, and electrolytic manganese, iron, cobalt, and nickel. Each button was remelted at least three times. The metals had a minimum purity of 99.9 pct except the nickel whose purity was 99.4 pct, the major impurity in this instance being cobalt. The preparation of the manganese alloys was attended by the customary difficulties associated with the vaporization of manganese. The technique used in this case was to add approximately 10 pct extra manganese to the original charge and to continue remelting the button until the final weight was in agreement with its intended weight. At least three alloys in each system were analyzed chemically and the results, even for the manganese alloys, were in good agreement with the intended compositions. A few additional alloys in the Ti-Mn-O system were prepared by the sintering of mixed powders in evacuated quartz tubes followed in some cases by arc melting. For annealing, the alloys were wrapped in molybdenum foil and placed in fused silica tubes containing zirconium chips. The fused silica tubes were evacuated at room temperature to a pressure of 1 x l0-6 mm of Hg and sealed. These capsules were then annealed for 72 hr at an external pressure of 5 x 10-5 mm of Hg in a vacuum furnace whose temperature could be controlled to + 1°C. The success of this procedure in avoiding significant oxygen or nitrogen pickup was indicated by the bright, ductile condition of the molybdenum foil and by the complete absence of a microscopic reaction layer on the specimens. This method did not permit rapid quenching of the specimens but in no case did metal-lographic examination indicate that a solid-state transformation had occurred on cooling. Metallo-

Jan 1, 1961

By E. S. Machlin

The kinetics of vacuum distillation, vacuum-melt surface reactions, crucible-melt surface reactions and boiling are analytically investigated. No disagreement with experiment is obtained upon applying a rigid flow model to describe the behavior of the melt in the vicinity of reaction surfaces. The theory focuses attention upon measureable parameters rather than upon the adjustable parameter, stagnant layer thickness, associated with other theories. The rigid flow theory is thus capable of quantitative evaluation and experiments to achieve this evaluation are suggested. KINETICS, rather than thermodynamics, often determine the degree of refinement achieved in vacuum melting. There is little understanding, however, of the kinetic principles involved in vacuum refining. This paper represents an attempt to achieve this understanding. There are two reactions which need to be con- sidered. The first is the refining reaction. The second shall be called the polluting reaction. It is the reaction associated with the introduction of components of the crucible into the melt. The mechanisms of both reactions are unknown. Many models can be constructed to describe either the refining or polluting reactions. For example, consider the refining reaction C + Q = CO(g). One model that can be imagined is that the carbon and oxygen combine in the melt to form CO which then diffuses to a melt-

Jan 1, 1961

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By R. H. Doremus

From measurements of carbide precipitation rates in a iron it was concluded that the carbides nucleated on dislocations in both strained and unstrained samples, except for the latter at lower temperatures and higher carbon concentrations, where there were more muclei than could form on the dislocations. The equation of Cottrell and Bilby for the segregation of atoms to dislocations was found to be inapplicable to this system. No satisfactory theory for the growth process is available. A study of the rate at which a second phase separates from solid solution can frequently reveal much about the mechanism of separation. There are still many features of the precipitation of carbon from a iron that are not understood, although this system has been examined extensively. To provide more insight into the mechanism of carbide precipitation in a iron, rates of this process were measured at different temperatures, carbon concentrations, and densities of dislocations in the iron. The concentra- tion of carbon in solution was followed from the height of the internal-friction peak; this height is directly proportional to the amount of carbon in solution and is not affected by the growing carbide particles. In this paper these rates are compared with those found by earlier investigators, and the mechanism of precipitation is discussed in light of these results as well as two earlier studies1, 2 and the electron microscopic work reported in the preceding paper. EXPERIMENTAL The amount of carbon in solution was followed by

Jan 1, 1961

By E. C. Stephens

The eastern Washington— Idaho clay region stretches along the northeast margin of the Columbia basin for 150 mil es. The three better known and developed clay areas are Clayton, Wash., (2 miles north of Spokane); Mica, Wash., (10 miles southeast of Spokane); and Moscow-Deary-Bovill, Latah County, Idaho (about 80 to 90 miles southeast of Spokane) see Fig. 1. Clays from the eastern Washington— Idaho clay area have been mined for more than 50 years. At present Mica, Washington deposits are used by the Gladding—McBean & Co. to make a variety of bricks and ceramic products and Latah County, Idaho clays are used by the A. P. Green Fire Brick Co. to make refractories. The Anaconda Co. made an intensive investigation of the clay deposits in the northeastern Washington-!daho area in 1919 to determine the existence of a supply of raw materials from which alumina could be made. The greater part of the work, which included systematic drilling and shaft sinking, was concentrated at Mica, Wash. This was part of a research project carrted on by the Anaconda Metallurgical Research Dept. under the direction of Frederick Laist and F. Frick and it was terminated in 4920. V. D. Perry, Vice President and Chief Geologist for The Anaconda Co., in 1952 assigned the writer to make a preliminary study of clay and other potential sources of alumina ore in the Pacific Northwest with particular emphasis on those deposits which might be of future importance to The Anaconda Co9s. then new aluminurri plant at Columbia Falls, Mont.

Jan 1, 1961

By D. S. Hutton, W. C. Leslie

Thermal etch patterns developed on poly crystalline 3.5 pct Si-Fe by heating in hydrogen or in argon have been examined. The most prominent feature of the etching is the development of striations on grains with (100) planes near the plane of the surface. These striations are probably produced by the resoution of a random, high-energy plane into (100) facets of lower energy. THE thermal etching of iron and iron-base alloys has a long history. The phenomenon was observed by Osmondl more than 70 years ago. The literature on thermal etching between that time and 1951 was reviewed by Olney,2 and a briefer review appeared in 1958. 3 The only articles which have been found dealing with the thermal etching of silicon iron are those of Dunn and Lionetti4 and of Dunn, Daniels, and Bolton,5 and they reported only grain boundary etching. EXPERIMENTAL PROCEDURES A cast 3.5 pet Si-Fe alloy was given a metallo-graphic polish and etch, then placed in flowing purified hydrogen for 6 hr at 2200°F. The same specimen was later repolished and etched to remove the thermal etching. The specimen was then held in flowing purified argon at 2200°F for 72 hr. In both instances the specimen was rapidly cooled by being pulled up quickly into the cold zone of the furnace. All photomicrographs shown are of the surface as removed from the furnace. Oblique illumination was essential for observation of the thermal-etching effects with a light microscope and was used for all the photomicrographs. RESULTS AND DISCUSSION Grain boundary etching, grain boundary movement, and contouring within grains are illustrated in Fig. 1. The contours within a single grain followed behind the advancing grain boundary. To determine the average contour interval, or step height, white light was used in an interference microscope. The steps were of the correct magnitude to separate while light into its spectrum of colors. A green light was focused at the top of a contoured area, shifting to red across the field. By using the difference in the dominant wave length of red and green light,6 and counting the number of steps across the area, it was possible to obtain a value of about 80A for the average step height. Laue back-reflection patterns of four grains with contour lines showed that the grains had a (100) plane slightly inclined to the plane of the surface (± 5 deg). Insofar as this could be determined from their irregular traces, the contour lines within a grain had a common direction, <100> ± 5 deg.

Jan 1, 1961

By W. J. Helfrich, C. L. Sollenberger

Many present direct reduction processes utilize iron ore concentrates for the production of sponge iron and the sponge iron is usually preferred as an agglomerate. Pelletizing a high grade iron oxide concentrate prior to reduction is a simple approach to the high capacity production of a uniform and agglomerated sponge iron product. The present paper describes the effect of different atmospheres and physical characteristics on the reduction of pelletized iron oxide concentrates. The kinetics of iron oxide reduction have been I studied by numerous investigators1-4 and a rate equation for the hydrogen reduction of hematite and magnetite has been proposed. Mc Kewan&apos; obtained kinetic data for the reduction of hematite spheres sintered at 13&apos;70°C (2498&apos;F&apos;). The kinetics of magnetite reduction was studied by Quets. He compacted the oxide at a pressure of 1 ton per sq cm and sintered the specimens to densities of 95 to 96 pct of theoretical. These studies demonstrated that the reduction of iron oxide is a topochemical process and that the rate of reduction is proportional to the receding surface area of remaining iron oxide. Thus, the measurement of the kinetics of iron oxide reduction depends upon the development of a measurable and well defined interface between metal and reacting oxide. It is evident that the reduction rate will be constant only when the rate of formation of the reaction product layer is constant. It was recognized by Joseph&apos; and Edstrom&apos; that the physical character of the oxide will determine the configuration of the interface between oxide and metal. The reduction of oxides which exhibit few pores or no interconnected pores should proceed by topochemical processes. However, if a massive or dense crystalline ore cracks during the reduction of the oxide, thus allowing the reduction to Proceed away from a well defined oxide/metal interface, then the observed reduction rate will vary or change during reduction. From a process standpoint, it would be difficult to apply absolute reduction rates determined for crystalline or nonporous iron oxide to the direct reduction of a porous pellet of iron ore concentrate. Most present direct reduction processes are attempts to utilize iron ore concentraates in the production of sponge iron. The sponge iron is usually preferred in an agglomerated form for subsequent melting practices. Pelletizing a high grade iron oxide concentrate prior to reduction is a simple approach to the high capacity production of a uniform and agglomerated sponge iron product. One process for preparing such a product has already been de-scribed. This paper describes the effect of different atmospheres and physical characteristics on the reduction of pelletized iron oxide concentrates. ORE CONCENTRATES STUDIED A magnetite concentrate from Reserve Mining Co. and a hematite concentrate from U.S. Steel Corp. were used in preparing pellets for these experiments. A head analysis of these concentrates is given in Table I. To compare the reduction rates of pelletized concentrates, it was necessary that each pellet contain equal amounts of oxygen which could be removed by reduction, regardless of the oxidation state, i.e., Fez% or Fe304. Also, because of the difficulty in preparing spherical pellets of uniform size, weight, density, and porosity for experimental purposes, pellets of a cylindrical shape were formed in a press.

Jan 1, 1961

By H. W. Fleming, R. R. Brooks

The Clearwater Deposit, a small occurrence of massive-sulphide mineralization enclosed in an envelope of disseminated-sulphide mineralization, was discovered as a result of an aeroelectromagnetic survey in New Brunswick in 1955. Subsequently, additional flights were made over the deposit and various ground follow-up methods were employed to ascertain the nature of their response. All methods proved to be capable of indicating the occurrence with varying degrees of precision. This paper is a presentation and a discussion of the magnetic and electromagnetic data, both airborne and ground, and the self-potential data obtained over this deposit. The attention of Canadian mining exploration companies was initially focussed on New Brunswick by the discovery, in 1953, of the Brunswick ore body. Ground electromagnetic surveys were of considerable assistance in locating and developing this deposit. In the following year, 1954, the Heath Steele base-metal deposits were discovered by employing an airborne electromagnetic device and ground electromagnetic surveys to follow-up the airborne indications. These discoveries demonstrated clearly that both airborne and ground electromagnetic techniques were applicable for locating the near-surface deposits of massive sulphides present in this region. Airborne electromagnetic equipment became available on a contract basis through Aeromagnetic Surveys Limited early in 1955 and was used extensively thereafter throughout a large portion of northern New Brunswick. It was as a result of one of these surveys with Aeromagnetic Surveys Limited equipment in the summer of 1955 that the Clearwater Deposit was detected. The airborne anomaly was located on the ground by means of an electromagnetic survey using a Swedish Slingram unit. During 1956, the region was investigated more thoroughly- in the hope that other sulphide bodies might be located. Airborne electromagnetic coverage was extended and the Clearwater Deposit itself was used as a testing ground for the various methods and types of equipment currently in use in New Brunswick. In this paper com prative data are presented for the airborne magnetic, airborne electromagnetic, ground magnetic and ground electromagnetic surveys over this deposit. The ground electromagnetic instruments used were the McPhar vertical-loop unit and the Slingram and Boliden horizontal-loop units. Self-potential surveys were carried out with a McPhar unit. From the geophysical point of view, all ground electrical methods employed indicated the presence and the extent of the massive-sulphide mineralization with a good degree of accuracy. The horizontal-loop methods however, defined the contacts more precisely as is to be expected when dealing with a flatly-dipping

Jan 1, 1961

By J. D. Meakin

The self-diffusion coefficients of ß tin have been deterttlltled using a plating and sectioning technique. The principal diffusivities pavallel and perpendicu1ar to the "c" axis are given by the Arrhenius relations Dc = 8.2 exp (-25,600/RT) sq cnl per sec and Da = 1.4 exp (-23,300/RT) sq cm) per sec. The results are discussed in terms of a vacancy mecharism of diffusion. In conjunction with an investigation of diffusion in dilute indium-tin alloys we have reexamined self-diffusion in tin single crystals. The published self-diffusion coefficients of tin, eensham&apos;) have always appeared anomalous in comparison to diffusion data for other metals and do not correlate with parameters derived from creep tests.&apos; In addition to the necessity of confirming the self-diffusion values for use in analyzing the alloy work, self-diffusion in an anisotropic lattice is of considerable fundamental interest and confirmation of the published data seemed worthwhile. For a crystal with an axis of symmetry three-fold or higher the diffusivity at an angle 6 to the axis is given by D? = (Da - Do) sin2?+ Do [1] where Da and Do are the principal diffusivities perpendicular and parallel to the axis. For a particular diffusion mechanism, again in a crystal of axial symmetry, these principal diffusivities are [2] Do - ? ?i2 COS?i In these expressions ?i is the displacement undergone by the ith atom and 8, is the angle this displacement makes with the symmetry axis. In this, as

Jan 1, 1961

By F. N. Ward, E. H. Bailey

Camp and sample-site methods useful for determining about 0.5 to 16 ppm of mercury in soils and rocks have been devised to complement the analytical methods already widely used in geochemical prospecting. In the camp-site procedure the sample solution is obtained by digesting the finely powdered sample with hot nine-molar sulfuric acid and bromine, the latter generated in place. The solution is buffered at a pH of 4 and the mercury is extracted into a relatively small volume of an organic solvent. Estimations are made by comparing the color of the mercuric dithizonate extracted from the sample with that extracted from a standard. In the sample-site method the mercury is volatilized as the iodide and the latter is dissolved in a buffer solution from which the mercury dithizonate is extracted as in the camp-site method. The estimation is made by a similar comparison with standards or by comparing the color of the mercuric dithizonate with artificial standards prepared from Orange II, an azo dye. Except for the establishment of standards, the time required by an experienced analyst seldom exceeds 10 min for a camp-site determination and 5 min for a sample-site determination. Camp-site determinations are useful for commodity studies and intensive exploration programs; sample-site determinations are applicable to extensive and reconnaissance-type geochemical prospecting programs. The results obtained on samples taken along traverses above known mercury ore deposits in the California Coast Range and western Nevada demonstrate the usefulness of both methods in geochemical prospecting. The increasing use of the mercury content of soils, rocks, plants, or water in geochemical prospecting emphasizes the need for analytical methods which are sensitive and at the same time require a minimum of readily available equipment. Sensitive methods based on the absorption of ultraviolet light by mercury vapor are common in the literature31 12. Although none of these methods have been used to analyze the large number of samples required in geochemical prospecting, they could be extremely useful except for the expensive instrumentation usually required to make the methods quantitative Also, such methods are perhaps too sensitive for field use, especially around areas of possible contamination. Other methods involve the distillation of mercury from a relatively large sample and subsequent collection of the vapors in nitric acid6. The mercury is then estimated by titration with a suitable reagent such as thiocyanate. These methods are not trace methods because the actual amount of mercury measured is often as great as 50 to 100 milligrams. Also, such methods are unsuitable for geochemical prospecting because of the amount of equipment necessary and the time required. Still other methods involve colorimetry, and the sensitive reaction between dithizone and mercury (11).. is the basis for a number of reports on the determination of mercury in biological materials 5,7. Moreover, by the judicious use of solvent extraction and suitable complexing agents, the dithiaone method can be made almost specific for mercury. However, none of the dithizone methods have yet been applied to the determination of mercury in soils and rocks. In most colorimetric methods he sample solution

Jan 1, 1961

By O. A. E. Jackson

In all three principal dunite dikes, minute disseminated grains of pyrrhotite are to be seen in the fresh rock in amounts less than 1 pct. Traces of nickel have been reported from many such specimens. Nickeliferous pyrrhotite is the principal nickel-bearing mineral, although olivine contains very minor amounts of nickel in solid solution, substituting for magnesium and iron. Such occurences are of no economic significance. Nickel analyses of possible economic significance (up to 3 pct Ni) have been returned from samples taken near the margins of the two large western dunite dikes. These samples were from schistose zones along and within the dike walls. The mineralized shear zones, up to 30 ft wide, strike N 30 W and dip from 65" to 90" west. They consist of layers of hard, fresh, green-gray dunite, mineralized with finely disseminated pyrrhotite. These layers alternate with layers of soft, black, oxidized schistose dunite up to 1 ft wide, well mineralized with pyrrhotite and tabular-fractured pentlandite in crystals up to 1/4-in. diam. Sulfides identified in polished sections were chiefly pyrrhotite and pentlandite, with much smaller amounts of chalcopyrite. There are two varieties of pyrrhotite. One develops a fine polish and conforms to published descriptions. The other is slightly darker and browner, does not polish as well, and displays flamelike growth or intergrowth structure when etched with nitric acid fumes. Pyrrhotite and pentlandite crystallized contemporaneously in the form of veins in the olivine and as fillings of the interstices of euhedral olivine crystals. Chalcopyrite replaces the other sulfides. The most striking feature of the deposits is their occurrence in intimately fractured and schistose zones in the dunite where faulting has been localized along the contacts of the sediments and the dunite dikes. Though far too little detailed work has been done to be certain, there appears to be a higher concentration of sulfides in the shear zones along the margins of dike apophyses, sediment reentrants, and strike and dip irregularities. Much more study would be required in order to submit a plausible theory of formation of the nickel deposits, supported by laboratory and field evidence. Results of the present study, especially localization of the metals by fracturing, certainly indicate that the nickel concentrations were brought about by precipitation of nickel sulfides from fluids that used the fractures as a means of ingress. Studies of nickel sulfide deposits throughout the world have demonstrated that such sulfides were deposited at considerable depths and at temperatures of several hundred degrees. This would rule out the possibility of groundwater as the transporting medium. The two possible sources of hot nickel-bearing fluids are quartz diorite and gabbro. The first possibility is that large volumes of fluids, expelled from the quartz diorite magma during its crystallization, obtained a supply of nickel by altering the nickeliferous olivine of the dunites. The likelihood of this process is lessened by the recognition that, although the dunites show some alteration to serpentine, talc, and trem-olite, they are for the most part remarkably fresh outside the schistose zones. The worldwide association of nickel with basic rocks, together with the presence of pyrrhotite in thin films on joint planes of the gabbro on Jumbro Mountain, favors the gabbro source. The writer extends thanks to C. Phillips Purdy, Jr., project chief of American Metal Climax Inc., for giving him the opportunity to study these deposits. He is also indebted to the officers of American Metal Climax Inc. and Discovery Mines Inc. for permission to publish this article.

Jan 1, 1961