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By K. Tanaka, J. D. Mote, J. E. Dorn

It) an attempt to ulLcoce.lP the operative strain-rate-contl-olliy: dislocation nieclzanistns, specially oviented sizgle clystals of the intel-nzediate 1zexagonal phase containing Ag plus 33 at. pct A1 were tested in tension over a wide range of temperatures. Slip was observed to take place by the {0001} <1120> {l100} mechani fracture took place across the(i100) plane and winning occurred by the (i01Z) ?lechanisn. Basal slip exhibited a strong yield point over the -alzge from 77 to 450°K, the upper ,esolved shear st]-ess having the exceptionally high value of 10,500 psi over this entire ?-a?zge of tenzpei,atuves. The critical 9-esolved shear stress for prismatic slip decreased f7-om 48,000 psi at 4.3"K to 23,000 psi at 170°K (Region 1) follozcirg zt:lzich it decl>eased sloz&ly to 21,500 psi at 475°K (Res&apos;on II); from 475" to 575°K (Regioz III), the c7-itical esolced shear stress dec&apos;-eased precipitously to 2000 psi; and from 575" to 750°K (Region IV) it decreased less afi&apos;dly to a low value of about 500 psi. Pvistintic slip in Region I was pobably controlled by the tliel-nally activated riecharzisui of nucleation and g,-ozcth of kinks in dislocations lying in Peierls potential troughs. In Region II for prismatic slip the critical 1-esolved shear stress was slzocn to be deteemined by sh0l.t-range 01-dering, Overall the forgiorz fo basal slip, 7.c.lre1-e a Strong yield-point phenorlienu ia7as observed, the critical vesolved slzea?-stress was shoztn to be determined by n conibirzation 0-f Szizuki locking and short-range-order Izavderzizg, The precipitous decrease in the critical resolved shear stress with increase in ter,/pe7-atrir-e over Region HI was tentatively ascribed to a decrease in the degree of slort-)ange 07-del;iqq (0)- clusteing) and also the effect of fluctuations the degree of o?der, It is at pgreser2t zrtzce)taitz as to 1t1hethe1- these or other possi1)le effects are also ,esponsible. fo- the data obsel-ved 172 Region IV. 1NTEREST in inter metallic compounds stems not only from their role in dispersion hardening of polyphase alloy ystems but equally from their potentialities for high strength, hardness, and stability not only at atmospheric temperatures but especially at elevated temperatures. As summarized in a re- cent symposium of the Electrochemical Society on "Mechanical Properties of Inter metallic Compound", most of the experimental evidence regarding the mechanical behavior of intermetallic compounds centers about the effect of temperature on the hardness and ductility of polycrystalline specimens. The available data reveal that the plastic behavior of intermetallic compounds might be rationalized in terms of the usual dislocation mechanisms appropriate to a solid solutions providing the additional complexities arising from crystal structure, long-range ordering, short-range ordering, and defect lattices are taken into consideration. It is apparent, however, in terms of the history on a solid solutions, that a complete detailed mechanistic rationalization of dislocation processes may not be possible until the deformation processes are studied in single crystals of intermetallic compounds. The present paper contains a preliminary report on the plastic behavior of single crystals of the hexagonal Ag-A1 intermetallic phase over a wide range of temperatures. The results confirm the thesis that single crystal data provide a most effective method of identifying operative dislocation mechanisms in intermetallic compounds. EXPERIMENTAL TECHNIQUES Several factors prompted the selection of the hexagonal Ag-A1 intermetallic phase for this preliminar investigation on the plastic properties of single crystals of intermetallic compounds: 1) This phase has a wide solubility range5 which would permit future investigations on the effect of composition and axial ratios on slip mechanisms. 2) Although it undoubtedly exhibits short-range ordering (or clustering) this intermetallic phase is free from complexities arising from long-range ordering.6 3) Since the atomic radii of aluminum and silver are practically identical, the possible complications due to Cottrell locking are minimized. 4)Whereas the dislocations on the basal planes are expected to dissociate into Shockley partials and are thus susceptible to Suzuki locking, those on the prismatic planes probably remain complete. 5) The axial ratio, being 1.61, is almost ideal, suggesting that short-range ordering may be almost spherically symmetrical. The present investigation was conducted exclusively with the hexagonal Ag-A1 alloy containing 33 at. pct Al. Preliminary investigations revealed that this alloy undergoes basal slip by the (0001)

Jan 1, 1962

By M. E. Nicholson

The solubility of carbon in Ni-Cu alloys was determined at 1000°C. The factors which limit solid solubility are discussed with particular reference to the influence of electronic factors. The results indicate the extent of solid solubility is a function of the density of states at the Fermi surface. THE solid solubility of an interstitial element is primarily limited according to Seybolt and Fullman1 and Speiser and Spretnak2 by (a) the strain energy produced when the solute atom takes its interstitial position, and (b) the partial molal free energies of the solid solution and the coexisting phases. In several binary systems of a transition and a noble metal, where there are no abrupt changes in strain energy or free energies of coexisting phases, the solid solubility of an interstitial third element drops abruptly to a negligible value at a composition corresponding to a complete filling of the "d-band." Such a decrease occurs in the case of hydrogen in the Pd-Ag system at 60 pct Ag.3,4 The solubility of carbon in Ni-Cu alloys seems to vary in a similar manner as indicated by the embrittling effect of carbon on these alloys. These al- loys are embrittled by slow cooling due to the precipitation of graphite. This embrittlement can be removed by heat treatment if the carbon content is less than the solid solubility limit at the heat-treating temperature. If the carbon content of the alloy exceeds the solid solubility at the heat-treating given temperxture, the embrittlement cannot be eliminated by solution heat treatment.&apos; Since pure nickel has a carbon solubility of 0.25 wt pct6 at 1000°C, embrittlement is easily removed from commercial nickel and nickel-rich alloys, which may contain of the order of 0.10 wt pct C. Embrittlement due to carbon cannot be removed from Ni-Cu alloys containing 70 to 80 wt pct Cu by annealing unless: the carbon content is of the order of 0.04 wt pct CL or less."&apos; Thus, it appears that the

Jan 1, 1962

By J. D. Vincent, Pierre R. Hines

INTRODUCTION OF FROTH FLOTATION INTO THE UNITED STATES "The introduction and development of the flotation process have proved to be of such momentous importance to the mining industry of the United States that they deserve to be considered historically ." T. A. Rickard l James M. Hyde installed the first froth flotation process in the U. S., about Aug. 1, 1911, at the Basin Reduction Co. plant, Basin, Mont., which was then under lease to the Butte and Superior Copper Co.2 Two months later, the Minerals Separation Ltd.. filed suit in the U. S. District Court of Montana against Mr. Hyde char& him with infringement of their Patent 835, 120/1906. The U. S. District Court decided in favor of Minerals Separation Ltd. on July 28, 1913. This decision was reversed by the Ninth Court of Appeals in San Francisco on May 4, 1914. Then the U. S. Supreme Court, on Dec. 11, 1916, upheld the patent on three counts only but restricted it to &apos;the use of less than one percent of oil.” The Miami Copper Co. was sued by Minerals Separation on Oct. 10, 1914, for infringement of Patents 835,120 and 962,678, and 1,099,699. The Miami Copper Co. was operating under John M. Callow&apos;s froth flotation process Patent 1,104,755/~uly 23, 1914. Miami lost this suit in the District Court of Wilmington, Del., and appealed to the Court of Appeals, Third Circuit, Philadelphia. The Third Court of Appeals decided against Miami, May 24, 1917. The case was referred to a Master and hearings to determine profit and damages were not settled until 1923. Nevada Consolidated Copper Co. was sued Sept. 9, 1919, and Magma Copper Co. was sued Jan. 10, 1920. Thus, the first ten years of froth flotation in the U. S. were beset by patent litigation. This litigation suppressed the free circulation of new discoveries or useful information that might be cited in a patent suit against the originator; it accounts for many of the blank spaces in the historical record. T. A. Rickard3 has reviewed the history of flotation and has given the chain of discoveries, patents, and processes that resulted in froth flotation. He has re- ported also on the patent litigation beginning in 1911 and ending in November 1923, when Minerals Separation&apos;s Patent 835,120 expired. He comments on

Jan 1, 1962

By D. J. Wynnemer, G. W. Preckshot

Precise electromotive force measurements have been made on the zinc-cadmium system over the temperature range 700° to 900°C. Activity coefficients, partial free energies, enthalpies, and entropies have been determined .for the entire composition range. The integral heat of mixing is positive and compares favorably with calorimetrically determined values. Vapor-liquid equilibrium compositions were determined .for a total pressure of 1 atm and these agree well with previous values determined in other ways. The use of electromotive force measurements to obtain thermodynamic data for liquid metal systems is a simple and well-known method. Several reviews of the various experimental methods and results have been published.2,3,11 However, most of the past work using this technique was carried out at temperatures slightly above the melting point of the alloy system where alloy composition changes due to vapor transport and increased metal solubility in the electrolyte are not important factors. One advantage of extending the electromotive force measurements up to and including the normal boiling point of the alloy is that it is then possible to evaluate the vapor-liquid equilibrium of the alloy at various pressure levels up to 1 atm. A detailed discussion of the thermodynamics of reversible electromotive force cells can be found in most advanced physical chemistry or chemical thermodynamic textbooks. The expression stating the inter-relation of the electromotive force and the thermodynamic functions is the Gibbs-Helmholtz equation.

Jan 1, 1962

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF&apos;-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By J. D. R. Neilsen

The objective of the research conducted and presented herein was to determine the effect of pre-established free gas saturation on the sweep efficiency of an isolated inverted five-spot well pattern. The investigation concluded that the ultimate recovery of an isolated inverted five-spot may be slightly increased by establishing a free gas saturation prior to water flooding; however, of more significance is the extreme deviation of the pattern's performance after water break-through from that commonly obtained from developed well patterns. The rapid "water-out" characteristic common to both linear floods and floods conducted in developed well patterns was not evidenced in the isolated inverted five-spot. Instead, the wells continued to produce oil long after breakthrough until ultimate areal sweep efficiencies of four, five, and six hundred percent were obtained prior to the water-oil ratio becoming excessive.

Jan 1, 1962

By C. H. Li, R. D. Carnahan, R. J. Stokes, T. L. Johnston

When silver chloride deforms by pencil glide at temperatures of 26ºand 72°C, grain size has no effect upon the proportional limit and the material necks down to a knife edge under tension. At -196ºC, deformation takes place on fewer slip systems to produce straight slip traces, the flow stress becomes sensitive to grain size and fracture occurs by cleavage from an intergranular source without any reduction in area. THERE are significant differences between the appearance of the slip bands formed in silver chloride and in the alkali halides at room temperature. The bands in sodium chloride, e.g., are fine and geometrically straight, whereas in silver chloride they are coarse and wavy.&apos; Such differences in the slip behavior prompted us to inquire what the effects of grain boundaries might be on the mechanical properties of these solids. As an introduction to a general study of ionic poly-crystal behavior, we have investigated the effect of grain size on the stress-strain relationships in silver chloride at different temperatures. We have chosen silver chloride chiefly because polycrystals can be easily prepared free from cracks and macroscopic voids by conventional techniques. Moreover, as we shall see, the slip behavior can be readily modified by changing the temperature. It will be shown that the effect of grain size on the yield stress of silver chloride is strikingly dependent upon the temperature of deformation and that this temperature effect comes about through a change in the number of slip systems which operate at the onset of plastic flow. EXPERIMENTAL PROCEDURES Polycrystalline tensile specimens were made by recrystallizing cold-rolled AgCl sheet. Thirty-gram quantities of AR grade silver chloride powder were melted in a low heat capacity furnace, cast into cylindrical forms 3/4 in. in dim and approximately 1 in. in length and then extruded with a 16:l reduction ratio into rods 3/16 in. in dim. Extrusion temperatures were varied from room temperature to 350°C. In order to impart various degrees of cold&apos;work to the extruded rod. All extrusions were then cross rolled to sheet 0.040 in. in thickness at room temperature and machined to form tensile specimens having a gage length of 0.750 in. with a width of either 0.250 or 0.145 in.* Annealing was carried out in an air oven at 200°C for periods up to 20 hr. specimens having average grain diameters ranging from 0.024 to 0.40 mm were prepared by varying the extrusion temperature and annealing time in the conventional manner. To obtain specimens with grain sizes larger than 0.40mm, lightly deformed thin prisims of silver chloride single crystals (supplied by Harshaw Chemical Co.) were recrystallized. Grain size determinations were made by an intercept method and revealed that the grains were equi-axed. Laue back-reflection X-ray patterns showed little tendency to form a preferred orientation texture. Specimens which were to be used for the slip band studies were polished by immersion in fresh boiling concentrated NH,OH for 60 sec. They were then etch polished for 10 sec on each side by hand lapping on a stationary velveteen lap wetted with a dilute Hypo solution (5 g of Kodak Acid Fixer in 100 cc H20). Finally the specimens were rinsed in warm water and alcohol, blown dry and carefully mounted in the tensile machine for testing. Tensile tests were performed at three temperatures, namely, 26º, -72º, and -196°C. A screw-driven hard tensile machine was used at a constant strain rate of 0.006 in. per in. per min. Loads were determined with a light- proof ring fitted with A-18 strain gages and extensions were measured with a 0.0001 in. dial gage. Constant level baths of alcohol with dry ice and liquid nitrogen were used to maintain the two lower test temperatures. EXPERIMENTAL RESULTS Reproducibility—In view of the light sensitivity and reactive nature of silver chloride, it was necessary to determine whether reproducibility depended upon either exposure to light or to the condition of the surface. However, during the course of the work it became clear that variation of laboratory lighting

Jan 1, 1962

By G. P. Contractor

Many factors affect the forge ability of steels. One of the major factors is chemical composition.' This article discusses the individual effects of alloying elements and the effect of the resultant modification of microstructure onforgeability. INTRODUCTION T HE use of alloy steels is expanding considerably and the fabrication procedures for such alloys are becoming more complex. An attempt is made in this article to describe the effect of alloying elements on the hot-workability of steels. Most of the data reported here are taken from the studies of Ihrig, Clark and others (Refs. 1-4). Chemical composition is not the only controlling factor. Grain size and surface condition of the material, forging temperature, and speed of deformation are also important. Certain conclusions can be drawn regarding the effect of various alloying elements on the hot-work-ability of forging stock. The results of hot-twist tests are considered useful in this connection as the number of twists to failure has been taken as the level of forgeability at a particular temperature. The peak in the "Number of Twists -Tem--

Jan 1, 1962

By J. J. Laffin

In the pursuit of comfort and safety, the wonders of science have given us controlled heating and cooling, thus enabling us to enjoy all the aspects of present-day living to an extreme never previously •envisaged. Man's attempt to conquer the elements largely involves con-trolling the temperature around him. Without having conquered this aspect, his body energy would be consumed in trying to maintain physical comfort, rather than being invested in the explorations which have resulted in man's control over the forces of nature. The indirect methods used to obtain the most agreeable temperature environment were developed because of the natural tendency to strive for increased safety, convenience and comfort. Until the twentieth century, when heat generated by atomic fission became a reality, man's only source of heat, except for that of the sun, came from his discovery of fire.

Jan 1, 1962

By L. J. Cunningham

I THINK it can be safely said that no mining operation, whetl1er open-pit or underground, is ever entirely free of water. It follows that every ton of ore bears a charge which represents, either directly or indirectly, the cost of keeping the mine workings as dry as possible. Water problems occur in all phases of mining operations. They cause difficult and costly drilling conditions during the exploration stage, they often seriously delay mine development, they can slow mine production and reduce efficiency, and they are a continued burden over the life of the mine. It is therefore in the interest of all mining men to be familiar with the methods and materials used for grouting. The most common grouting material is cement. Cement grouting is old and well established, and many engineers are familiar with its uses and limitations. The technique of cement grouting is relatively simple and fairly well understood, and the materials utilized are relatively in-

Jan 1, 1962

By John W. Cahn, John E. Hilliard

Single crystals of copper and silicon-iron were cold rolled in orientations chosen to produce individually the major components of the poly crystalline deformation texture. The orientation dependence of the recrystallization kinetics was studied relative to the primary recrystallization textures of these specimens. It is not possible to rationalize the poly crystalline re crystallized textures on this basis. The results suggest an important role of the interaction of adjacent crystals during the deformation of aggregates. BRICK and Williamson1 first noted evidence that the recrystallization temperature was different for straight-rolled and cross-rolled copper given comparable reductions. Michalak and Hibbard2 investigated quantitatively the effect of rolling procedure on the kinetics of recrystallization of cold-rolled copper and found that material cold-rolled the same amount by straight-pass, cross-pass, and compression-pass techniques developed different deformation and recrystallization textures, different 1-hr recrystallization temperatures, and different recrystallization kinetics. However, the temperature dependence of the rate of recrystallization was essentially the same for all techniques. Similar results were obtained on iron. Dunn and Koh3 in studying the recrystallization textures of cold-rolled silicon-iron single crystals reported large differences in the annealing temperatures and times required to recrystallize specimens of different orientations cold-rolled the same amount. Liu4 and Liu and Hibbard5 utilized the concept of different recrystallization temperatures for different orientations of cold-rolled crystals to rationalize the difference in recrystallization textures found in various face-centered-cubic metals. Their explanation predicted a significant difference in the recrystallization kinetics of deformed (110) [112] crystals as compared to (358) [352] crystals, and, in fact, Liu4 reported evidence that this difference existed at least qualitatively. Verbraak6 who rolled and recrystallized a series of copper single crystals found that the double (112) [111] rolled orientation is related to recrystallized cube texture formation. The effect of rolling intensity on the relative amount of cube component suggests an important role of recrystallization kinetics. Walter and Hibbard7 while trying to relate the behavior of rolled and recrystallized single crystals of silicon-iron to the behavior of polycrystal-line silicon-iron again noted that differences in recrystallization kinetics were necessary to rationalize their results. The purpose of the present investigation was to obtain quantitative kinetic data on the recrystallization of single crystals of both copper and silicon-iron rolled to initial isolated individual orientations corresponding to those found in the polycrystalline deformation textures. These data might indicate the importance of the deformation orientation, i.e. the range of available nuclei, the deformed matrix orientation into which these nuclei grow, and the orientation dependence of their growth rate during primary recrystallization on this texture. I. COPPER Experimental Procedure—A single crystal of 99.98 pet purity copper, grown by the Bridgman technique, was purchased in the form of a bar 1 1/2

Jan 1, 1962

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit &apos;flash&apos; chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om&apos;nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.&apos; One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.&apos; By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By P. E. Doherty, B. Chalmers

Subboundaries may be revealed in aluminum by the formation of pits on the surface during cooling from elevated temperatures. The pits do not form in the vicinity of high- or low-angle boundaries. They are attributed to the condensation of vacancies from a super saturation produced during coolirzg. Using the vacancy pit and Schulz X-ray techniques for observing low-angle boundaries, a study was made of the transition from the nearly perfect seed to the striated structuke characterist-ic of aluminum crystals grown from the melt. It was found that the individual striation boundaries develop by the coalescence of very small-angle boundaries, as well as by the addition of individual dislocations. Several mechanisms for the formation of striations are discussed. Evidence was found suggesting that a super-saturation of vacancies exists near a growing interface, and it is proposed that the resulting climb of existing dislocalions produces "half&apos;-loops" at the interface, which combine to form the low-angle striation boundaries. LINEAGE, or "striation" boundaries, have been studied in detail by Teghtsoonian and Chalmers 1,2 in crystals of tin grown from the melt, and by Atwater and Chalmers3 in lead. They found that single crystals grown from the melt consist of regions which are separated by subboundaries that lie roughly parallel to the growth direction. A difference in orientation of 0.5 to 3 deg exists between the striated regions; the misorientation is such that the lattice of one region could be brought into coincidence with the lattice of its neighbor by a rotation about an axis approximately parallel to the direction of growth of the crystal. They observed an incubation distance for the formation of striations which increased with decreasing growth rate. They also found that in any crystal, the sum of all rotations of the lattice in one sense, in going from one striation to the next, is very nearly equal to the sum of all the rotations in the opposite sense. A striation boundary, which is a low-angle grain boundary, can be described as an array of dislocations. If it is assumed that suitable dislocations are introduced into the crystal during solidification, the formation of striation boundaries can be explained as a result of the migration of the disloca- tions into arrays. The formation of arrays is energetically favorable since the energy of an assembly of dislocations can be reduced by the interaction of the stress fields when a suitable array is formed. This investigation presents and interprets new information concerning the nature and origin of striation boundaries in aluminum. EXPERIMENTAL TECHNIQUE Single crystals of high-purity aluminum (Alcoa 99.992 pct) were prepared by horizontal growth from the melt.&apos;&apos; The specimens were subsequently electropolished in a solution of 5 parts methanol to 1 part perchloric acid kept between -10° and 0°C in a bath of dry ice and alcohol. The current density was approximately 6 amps per sq in. Doherty and Davis9 have shown that in aluminum sub-boundaries with misorientations of not less than several seconds of arc may be revealed by the vacancy pit technique. During cooling from elevated temperatures pits form on electropolished surfaces of aluminum crystals as a result of the condensation of vacancies.11 Pits do not form in the vicinity of small- or large-angle grain boundaries, presumably because such boundaries act as sinks for vacancies. Boundaries of misorientations down to 3 sec of arc are revealed as pit-free regions, see Fig. 1. The Schulz X-ray technique12 was used to determine the angular misorientations of subboundaries. In this method, white radiation from a micro-focus X-ray tube is used to produce an image of a fairly large area of a single crystal surface. Subboundaries cause splitting in the diffracted image, see Fig. 2. Misorientations down to about 15 sec of arc may be observed with this technique. OBSERVATIONS AND DISCUSSION Figure 1 shows a striated aluminum crystal grown at 10 cm per hr etched by the vacancy pit technique. An incubation distance of about 1 cm is observed before the initiation of striation boundaries. Fig. 2 is a Schulz X-ray photograph of a striated crystal similar to that shown in Fig. 1. A large area of the crystal was studied by means of a series of photographs. Fig. 2, which is a reflection from the (100) plane, included about the first 4 cm of crystal to freeze. There is an incubation distance of about 1 cm, and a distance of about 2 cm over which the angle of misorientation builds up to its final value of approximately one degree. Some twist component can be seen in Fig. 2 at the right side of the photograph. From Fig. 2 it can be seen that the sum of all rotations of the lattice in one

Jan 1, 1962

By J. G. Haymes

This report by the Bureau of Mines is the first of two proposed papers on evaluation of spectrophotometric, spectrographic, polarographic, and other analytical methods for quantitatively determining impurities in high-purity tungsten. Some of the methods described are standard methods that have been successfully applied to determine low-level impurities, several are modifications of known methods, and some procedures are entirely original. The Bureau of Mines is actively engaged in tungsten research because tungsten has an extremely high melting point, in fact the highest of any known metal. The metallurgist must know the content of impurities in tungsten because of the marked effects even micro amounts of impurity elements have on its physical properties. The Bureau procured a number of analyzed samples of above-average purity from research laboratories of companies engaged in production and fabrication of tungsten. These samples were investigated by the analytical procedures of those companies for several metallic impurities. Subsequent analytical laboratory determination of impurities in these samples agreed with the analyses as reported. With this assurance that analytical methods were basically accurate for metallic impurities, procedures for the determination of several of these elements were modified to lower the limits of detection and increase the sensitivity of methods. Carbon and the gases hydrogen, nitrogen, and oxygen were determined by standard instrumental methods, modified to provide greater sensitivity for reliable determinations when content of these elements was low. After the reliability of the modified procedures was affirmed, they were used as a product evaluation guide in the development of a vapor-plating technique for the production of high-purity tungsten. The following list of elements can be determined by one or more of these methods: AI, B, Be, Ca, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, S1, Sn, Ti, V, and Zn. In addition, a vacuum-fusion method for the determination of H, N, and 0, and a conductometric method for carbon are described. Lower limits of determination and detection for each element listed are given.

Jan 1, 1962

By V. F. Swanson

As part of the Bureau of Mines titanium resources examination program, samples of altered rock (saprolite) and unaltered rock from the Roseland anorthosite near Roseland, Nelson County, Va., were tested for amenability to beneficiation by flotation. A flotation technique was developed to produce bulk concentrates of ilmenite, rutile, sphene, and leucoxene. It was necessary to first float apatite using oleic acid as the collector, in an alkaline pulp with dextrine as a titanium mineral depressant. The titanium minerals could then be floated from the apatite tailing, using fluosilicic acid to depress the remaining apatite, morin to depress ferromagnesian minerals (when present), and oleic acid as the collector. A bulk titanium mineral concentrate, analyzing 66.0 percent Ti02 and 0.08 percent P205, was obtained from a sample of the unaltered rock which contained 5.45 percent TiO2 and 2.81 percent P205. Overall recovery in the concentrate was 47.1 percent of the total TiO2 in the ore. About 55 to 65 percent of the saprolite sample was clay and was removed by attrition scrubbing and decantation. The apatite prefloat procedure was applied to the saprolite sands; subsequent titanium mine: 1 flotation recovered 72.2 percent of the Ti02 in a bulk concentrate containing 65.1 percent TiO2 and 0.20 percent P205.

Jan 1, 1962

By I. C. Edwards, D. C. Smith

THE milling plant of Bicroft Uranium Mines Limited at Ban-croft, Ontario, was one of the first in Canada to employ ion excl1ange for the selecti1•e recovery of uranium from acid leach liquors. The ion ex-change circuit started operating early in November, 1956, and by June 1 I959, had handled more than two million tons of pregnant solution containing I,830,000 pounds of U3Os. Each column had been saturated and eluted about 430 times. The ion exchange columns are the conventional fixed bed type. Uranium is eluted from the resin with a sodium chloride-sulphuric acid solution and is precipitated continuous-ly with magnesia. After filtering and drying, the precipitate, or "yellow cake," is packaged in drums for shipment to the refinery.

Jan 1, 1962

By Pierre R. Hines

The first progress in American ore dressing practice was made in the mills of the Mother Lode in Calif., the Comstock Lode in Nev., and Gilpin County in Colo., during the years 1861 to 1870, when the ancient wooden stamp battery, with square wooden stems, was converted into the &apos;California&apos; stamp made of wrought and cast iron, with round stems which rotated. Eli Whitney Blake invented the jaw crusher in 1858 for stone crushing, and it was soon used for crushing ore. F. W. Gates&apos; gyratory crusher followed twenty years later. S. R. Krom, Thomas A. Edison, and others improved the Cornish rolls by increasing their size and spring pressures; the Symons Brothers made horizontal and vertical disc crushers; W. Ball and E. T. Leavitt designed powerful steam stamps for Lake Superior native copper ores; and jigs were mechanized. William B. Frue, a mill superintendent in the Lake Superior copper district, invented the vanner in 1874. Arthur F. Wilfley built his riffled concentrating table in 1895, just after Dr. Robert H. Richards commenced his Ore Dressing. The Wilfley table so changed concentrator flow sheets that Dr. Richards was compelled to revise his text, and its publication was delayed until 1903. The value of sizing or classifying before concentration was recognized. Dr. Richards had persuaded the Anaconda Copper Mining Co. to install round tables with special surfaces to catch the &apos;extremely fine free mineral.&apos;l Gravity concentration had achieved almost every refinement for recovering or separating minerals by the difference in their specific gravities. However, one serious problem remained unsolved, i.e., how to retrieve the enormous loss of the extremely fine mineral in the slime portion of the ore. Slime, then, as now, was not a precise term due to the variation in the mineral composition of the ores and the different requirements in crushing, grinding, sizing, and classifying. At that time, slime was considered to be fine sand and colloidal material passing 100 mesh.2 Most sulfide ore minerals are more friable than their associated gangue minerals, so that crushing and grinding increased the proportion of the extremely fine ore minerals in the slime. Sparkling specks of galena, chalcopyrite, argentite, or ruby silvers, according to the ore, floating away on the tailing stream from vanners and slime tables, were familiar sights in the old gravity concentrators. Gravity concentration practice was aimed at recovering the ore minerals at the coarsest possible size because the recovery was higher and unnecessary

Jan 1, 1962

By J. M. Dahl, R. J. Warrick, O. K. Riegger, H. Van Vlack

A liquid which is rich in oxygen (and silicon) develops at steel rolling temperatures in resulfurized and plain-carbon steels. This liquid fluxes solid manganese sulfide. The composition of the liquid and the resulting microstructures vary with the manganese/silicon/oxygen ratios in the steel. The observations and conclusions zuhich are presented are used 1) to suggest a mechanism for MnS deformation in resulfurized steels, and 2) to rationulize hot-shortness anomalies between plain-carbon and resulfurized steels. 1 HIS is a summary of the dependence of sulfide inclusion microstructures upon steel composition, and an interpretation of the behavior of sulfide inclusions at steel-rolling temperatures. Sulfide inclusions are known to have several metallurgical effects upon steel. Their effects upon hot-shortness are best appreciated. Although hot-shortness is well known, it is questionable whether its mechanism is fully understood because there are several anomalies in our interpretation. For example, why should not high sulfur contents produce extensive hot-shortness in free-machining steels ? A second metallurgical consequence of sulfide inclusions appears because sulfide inclusions improve machinability. Furthermore, globular inclu- sions are to be desired over elongated inclusions. To date, we know that lower silicon contents (< 0.010 pct) favor the globular sulfides, but we do not know why this interrelationship between silicon content and inclusion shape exists. Finally, the evidence is strong that the surface quality of a hot-rolled steel is particularly sensitive to the sulfur content. SUMMARY OF PREVIOUS WORK The role of sulfur in hot-shortness was first suggested during the past century. It is uncertain who was the first to conclude that sulfur was less deleterious in the presence of manganese, and that manganese altered the sulfide phase from a liquid FeS to a solid MnS at steel-rolling temperatures. However, Urban and chipman&apos; emphasized that liquid FeS may accumulate as an interdendritic film during solidification. More recently, Keh and Van lack&apos; showed that the intergranular liquid does not completely surround the metal grains at all rolling temperatures. Rather, a small finite dihedral angle exists when geometric equilibration is attained at

Jan 1, 1962