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By P. E. Cavanagh

"The Davis tube test has been used for many years as a laboratory method for determining the magnetic iron re-coverable from a magnetite iron orebody. This paper de-scribes a method for determining the recoverable iron from ores of the Labrador Trough type, with the usua1 flow sheet utilizing spirals followed by magnetic separation.The mechanical structure of a metamorphosed iron ore, resulting from recrystallization over long periods of time, is the basis for the laboratory method developed. Similarities between the structures of such recrystallized ores and the structure of annealed and recrystallized steel are noted.A laboratory technique to determine the size of the different grains of gangue and iron ore minerals is de-scribed and the application of this information to arrive at recommended grinding techniques and flow sheets is demonstrated. The use of the method to determine recoverable iron in such ores is compared to actual iron recovery in the pilot-plant and commercial concentrations of the same ore.The use of a specified lower limit of recoverable iron as determined by this method, in order to design open-pit limits, achieves practical results when compared to designing a pit based on an arbitrary lower limit of total soluble iron. The Ungava Iron Ore deposits are used in giving an example of the resulting pit design changes."

Jan 1, 1968

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968

By Samuel J. Sims

The Grace mine magnetite deposit, located 2 miles north of Morgantown in Berks County, Pennsylvania, was discovered in 1948 by an aerial magnetometer survey. It is situated on the southern border of the Triassic lowlands section of the Piedmont province. Cambrian sandstones, shales, and limestones overlie Precambrian crystalline rock and were folded and thrust-faulted during the late Paleozoic Appalachian revolution. Late Triassic continental sediments were deposited on the deformed basement rocks and were intruded by Late Triassic diabase dikes and sills before regional tilting and normal faulting occurred. The Grace mine magnetite ore is characteristic of the Cornwall type. The ore has replaced a Cambrian limestone lens isolated between Triassic diabase footwall and Triassic sedimentary rock hanging wall. The ore body is roughly tabular in shape, dips 20° to 30°NE and plunges about 20°N80°E. The ore is granular, fine- to medium-grained, typically consisting of unevenly distributed magnetite in a matrix of light green to white serpentine gangue. Magnetite is the major ore mineral, pyrite and chalcopyrite are common accessory minerals, and pyrrhotite occurs locally. Sphalerite, marcasite, galena, hematite, digenite, and goethite are uncommon. Serpentine, talc, and chlorite are the major gangue minerals; calcite and dolomite are common, and phlogopite, tremolite, and biotite are present locally. Apatite is a common accessory; sphene is rare. Calcium-magnesium silicates were formed first by contact metamorphism of impure limestone by the intruding diabase. Later, the silicates were altered hydrothermally to the serpentine- talc-chlorite assemblage now present. Magnetite, the first ore mineral, formed by replacing serpentine and was followed by pyritepyrrhotite and then by chalcopyrite-galenasphalerite. Marcasite, secondary pyrite, goethite, and hematite are secondary minerals resulting from alteration of pyrrhotite and magnetite. It is estimated that confining pressure was about 1500 bars and the temperature range was 500° to 675°C during ore formation.

Jan 1, 1968

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

By V. K. Grotzky, F. J. Fraikor

A number of investigators have noted the importance of various precipitation reactions on the properties of commercial-purity beryllium.1-5 Carrabine, for example, has demonstrated the interaction of iron and aluminum on the mechanical properties of hot-pressed polycrystalline beryllium.6 He considered the determining factor on elevated-temperature properties to be a reversible AlFeBe, precipitation reaction which could be directly related to the Fe/Al impurity ratio of the beryllium. Any aluminum in excess of the stoichio-metric amount required to form A1FeBe4 was presumed to remain primarily in the grain boundaries. We have observed, by transmission electron microscopy, such a grain boundary effect after various heat treatments of beryllium sheet. The starting material in this investigation was bare-rolled beryllium ingot sheet (0.001 to 0.005 in. thick), in contrast to the hot-pressed powder utilized by Carra-bine. It should be noted from the ingot sheet analysis shown in Table I that the Fe/Al weight ratio was near unity which would provide some free aluminum although the total aluminum and iron content was still small. Fig. l(a) shows some aluminum or aluminum-rich precipitates in the grain boundaries of a beryllium foil which had been quenched from 1200°C into brine at -TPC. Similar grain boundary precipitates were found, particularly at grain boundary intersections, in other samples quenched from 1100° and 1000°C. The length of annealing time at these elevated temperatures did not appear to substantially alter the amount of grain boundary precipitates, thus attesting to their relative insolubility. No matrix precipitates were observed other than the normal BeO and Be2C inclusions. A microprobe analysis of the larger precipitates at

Jan 1, 1968

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of' cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi'e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600'F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.' Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.'-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors' laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:'-'' the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

By D. A. Elgillani

Oxidation potentials have been measured in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and ethyl xanthate at various values of pH and related to flotation response. Eh-pH diagrams are constructed and show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide in the depression of pyrite with xanthates as collector has been the subject of many investigations (1,2,3,4,5,6), and from these studies several theories on the mechanism of depression have evolved. Wark and Cox (7) and Gaudin(8) have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues (9,10,11) have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland (12) has shown that both of these theories describe accurately the relation between pH value and cyanide addition at constant collector addition but fail to describe the relationship, between pH value and the amount of collector required to cause flotation. Taggart(12) suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar(4,6) has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg/liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10; these results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface.

Jan 1, 1968

By R. J. Schaefer, M. E. Glicksman

Direct, in situ observation of metallic alloys during solidification reveals that in some systems crystal multiplication occurs by means of a dendrite remelt-ing process, without the necessity of independent nu-cleation events. The solidification is observed on optically clean surfaces of supercooled molten alloys. In one system (Sn-3 wt pct Bi) , a fine-grained equi-axed structure is produced by the complete disintegration, via remelting, of transient initial dendrites. In contrast, several other metallic systems show little or no evidence of remelting activity. The behavior of these metallic systems is consistent with that expected on the basis of published observations of dendrite remelting in transparent organic alloy systems. It is concluded that dendrite remelting is an important crystal multiplication process in some metallic alloys, but is velatively unimportant in some other alloys. The detachment of dendrite branches from the primary stem by a remelting process has been observed by Jackson, Hunt, Uhlmann, and seward1 during the solidification of some transparent organic alloy systems. The branches released by this remelting process can drift free of the primary stem and serve as seeds for the formation of numerous independent crystals. This proliferation of new crystals does not require repeated independent nucleation events, but only modification of the initial solidification structure. The mechanism of dendrite remelting, as described by Jackson et a1.1 and by Tiller and O''Hara,2 is dependent on the transport of both heat and solute and is, therefore, expected to operate only in alloys, and not in pure substances. It was found in the transparent organic alloy systems that remelting occurred primarily in the constricted regions near the base of dendrite branches, where the branches had grown through the solute-rich liquid layer surrounding the primary dendrite stem. It was suggested that impure solid had formed in these constricted regions at a relatively low temperature and had later become unstable as further solidification of purer material raised the temperature. Jackson et al. proposed that the equiaxed zone of metal alloy castings originates from a similar remelting process, and they demonstrated the operation of this mechanism in "ingots" poured from saturated salt solutions. Although these substances were especially selected to show solidification behavior similar to that of metals,3 the remelting mechanism has, until now, been subject to the objection that its operation has not been directly observed in a metallic system. Considering the fact that thermal properties such as diffusivity may differ by as much as two or three orders of magnitude between metals and organic compounds, this objection was considered to be possibly serious. A method has now been developed by which it is possible to make direct optical observations of metals during solidification. This method has revealed transient solidification processes which would not be detected by metallographic examination of totally solidified specimens. In particular, a grain-refinement process in a metallic alloy has been observed to be a direct consequence of the total disintegration of an initial dendritic structure. The influence of an initial, transient solidification structure on the final solidification structure is demonstrated here for the first time in a metallic system. I) EXPERIMENTAL The technique of using a transparent flux to maintain an optically clean metal surface during solidification has been described by us elsewhere.* The

Jan 1, 1968

Unfortunate occurrences resulting in injuries, loss of life, and destruction of property by explosion, fire, and other mishaps during shaft sinking focused the attention of the Bureau of Mines on the need for safety standards For such operations. Information Circular 7810 was published to meet that need. The current revision updates and replaces IC 7810. Several States have some rules and regulations applicable to local conditions, and several Bureau publications (including some now out of print) cover the hazards that may be encountered in shaft sinking. Certain requirements of the Federal Mine Safety Code and Federal Coal Mine Safety Act may be applied, but there are no definite, uniform standards that will guide those desiring to sink a shaft safely and bring about uniform safety inspections.

Jan 1, 1968

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3') a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;' hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.' This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968

By J. M. Woodall

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

Jan 1, 1968

By J. L. O’Brien, M. Suenaga, K. M. Ralls, V. F. Zackay

The effecls of aging a1 400°C on tile resistive transition at 4.2°K of a superconducling 70Zr-30Nb alloy are reporled. Microstrclural changes were studied by critical temperature, resistiue critical field, residual resistiuily, and microhardness measurements and by X-ray diffraction, optical microscoby, ad replication electron microscopy. The result of the aging treat- A defect-free Type 11 superconductor in a magnetic field above Hc1 cannot sustain a transport current runt is a fine array of w-phase pavticles with a mean center to center interparticle spacing of about 800A. At an aging time of 300 hr the maximum onset critical current density is rcached. The particle size at the maximum current density if about 4202. At times longer than 300 hr effective particle impingement leads to lower onset critical current densities. perpendicular to the applied field without power loss in the sample.&apos;-3 This power loss is due to flux line motion caused by the Lorentz force and is manifested by a longitudinal voltage.4-6 When defects are present in the material, flux lines are pinned until the Lorentz force exceeds the "pinning force". That is, it is thought that flux lines reside in free-energy wells existing at the defects, and the critical Lorentz force is that which when integrated over distance will supply the free-energy difference necessary to move the flux

Jan 1, 1968

By Marvin P. Barnes, John G. Simos

The Park City District, Utah, is situated in the Wasatch Range at the intersection of the westward extension of the axis of the Uinta Range. Ore has been mined almost continuously from the first discovery in 1869 to the present day, with a total production of over 14 million tons. Sediments of Carboniferous to Triassic age have been folded into the northerly plunging Park City anticline and subsequently modified by thrust faulting, diorite and diorite porphyry intrusions, and strong east-west normal faulting during the Laramide orogeny. Younger andesitic volcanics partially cover the eastern edge of the district. The ore bodies occur as both lode and bedded replacement deposits over widely scattered localities. Near surface, high-grade silver "bonanza" ores were mined in early days from the Ontario and Daly Lodes, which occur along the east-west zone of faulting near the center of the district. Other lode or fissure deposits were found along the Mayflower and Hawkeye faults to the east and southeast. Large bedded replacement silver-lead-zinc ore bodies associated with east-west zones of fissuring, have been mined from favorable horizons in the Park City Formation in the Daly West and Judge mines. A series of long, narrow, high-grade, replacement ore bodies occur in the Silver King mine at a single horizon in the Park City Formation. Ore is currently being mined from strong bedded replacements in the Humbug Formation near the apex of the Park City anticline. Factors controlling ore deposition are: magmatic source, structural feeder systems, and favorable host rocks. Ore deposition along favorable beds is primarily a function of physical conditioning and secondarily of chemical composition.

Jan 1, 1968

By R. S. Fowkes

Jetstream pressure distributions and coal cutting rates were determined for a number of nozzles and under different operating conditions. The jetstrearn pressure distribution data were fitted to an assumed curvilinear equation by the utilization of a numerical least-squares technique with the aid of a digital computer. Subsequent manipulation of the approximation equation showed that the total force of the jetstream, rather than its maximum pressure or total kinetic energy per unit Lime, was the most significant quantity affecting the coal cutting rate. A shorter method for assessing the ability of a nozzle to cut coal was found.

Jan 1, 1968

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, &apos; for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

By Robert E. Barieau

A list of 163 references to original experimental PVT data on helium is presented for the period 1895 to 1968. The list is complete as of the start of the Helium Centennial Year, 1968, to the best of the author&apos;s knowledge. Citations were keypunched for easy updating and are listed alphabetically by author.

Jan 1, 1968

By Richard H. Bube

Photoelectronic radiation detectors may be conveniently classified as homogeneous intrinsic, homogeneom extrinsic, or junction type. Highly photosensitive homogeneous intrinsic photodetectors may be prepared from a number of different II-VI, III-V, or IV materials. Such materials require the presence of specific imperfections that can act as sensitizing centers to provide long majority carrier lifetime. Homogeneous extrinsic photodetectors are of interest primarity for infrared detection, and consist principully of germaniuim and silicon with suitable inpurities. A vaviety of junction photodetectors exist, with silicon us the most common material for them all. The following extrema in performance are found: 1) highest photoconductivity gain in homogeneous intrinsic photodetectors; 2) smallest response time (highest frequency response) in p-i-n junctions; 3) largest gain-bandwidth product in avalanche diodes. ALTHOUGH the total number of materials exhibiting photoconductivity effects is very large, only a relatively few of these have appropriate properties for a practical photoelectronic radiation detector. In fact if one surveys the commercial detectors currently available, one finds that the field is dominated by some ten or fewer materials. These are summarized in Table 1 in terms of the other important variable in detector fabrication, the structure of the material, i.e., whether the material is used as a single crystal or in polycrystalline form, and whether the material is used as a homogeneous detector or whether the detector depends upon the existence of a junction or barrier in the material. The principal wavelength range for each type of material is also shown, together with an indication of the utilization of intrinsic or extrinsic excitation. For the purposes of the present comparison of various detectors, it will be convenient to discuss two main topics: homogeneous photodetectors and junction photodetectors. The performance of a photoelectronic radiation detector is measured in terms of two parameters: the photoconductivity gain, and the response time of the detector. A convenient figure-of-merit is given by the ratio of gain to response time, often called the gain-bandwidth product. The photoconductivity gain is a device parameter since it varies in many cases with the applied voltage and the detector geometry, and should be distinguished from the actual photosensitivity of the material involved. This photosensitivity can be conveniently given as the product of free carrier lifetime and mobility in the material. The photoconductivity gain is defined as the number of charge carriers which pass between the electrodes per second for each photon absorbed per second, where G is the photoconductivity gain, is the pho-tocurrent in amperes, e is the electronic charge in coulombs, and F is the total number of electron-hole pairs created in the photo conductor per second by the absorption of light. The gain may also be expressed as the ratio of the lifetime of a free carrier to the transit time for that carrier, i.e., the time required for the carrier to move between the electrodes. For a material in which one-carrier conductivity dominates, where T is the lifetime of a free carrier, ttr is the transit time for this carrier, p is the carrier mobil-ity, V is the applied voltage, and L is the electrode spacing. From Eq. [2] it follows that the photoconductivity gain is proportional to the photosensitivity of the material (tP), the proportionality constant being The photosensitivity of a material, and hence the photoconductivity gain of a device utilizing the material, depends on the lifetime of the free carriers as a critical parameter. In a homogeneous material this lifetime is determined by the nature of imperfections in the material, and in an inhomogeneous material the lifetime is determined by the specific junction structure. The speed of response, the other basic photodetec-tor parameter, is determined by factors quite similar to those important for photoconductivity gain. Imperfections are of primary importance in homogeneous materials, and the structure of the junction is a determining factor in junction devices. For infrared detectors it has become common to define another quantity designed to indicate directly how effective the detector is in distinguishing between a small photoconductivity signal and random noise due to the detector and its environment. The detectivity D* is given by

Jan 1, 1968

By Sabri Ergun

This report gives the result of investigations of coals of different rank, coal com¬ponents, chemically and thermally treated and irradiated coals, and sedimented organic matter. In most studies the arbitrary parameters obtained from the usual quantitative profile analyses are not given largely because they lack physical meaning. Instead comp interpretations are offered. X-ray patterns of high-volatile bituminous and lower rank coals are not self¬-sufficient for structural interpretation by the methods of analysis developed to date. The patterns of hydrogenated and dehydrogenated coals indicate that the basic change in the structure of bituminous coals with increase in rank is the conversion of alicyclic structures into aromatic layers. In low-rank anthracites the aromatic layers are about 10 A in size. The increase in rank is the result of coalescence of layers. High-rank anthracites have layer sizes of 25 to 40 A and exhibit the development of three-dimensional (hkl) reflections of graphite, indicating ordering of adjacent layers. In meta-anthracites the layers are > 1000 A and the basic structure is that of defective crystalline graphite. The well-known petrographic components in low-rank coals have different structures; the differences dissappear in low-volatile bituminous and higher rank coals. The patterns of sedimented organic matter, except impsonites, differ from those of coal hydrogen contents are high, and their X-ray patterns are consistent with those of structures. In contrast to normal coals, the patterns of uranium-bearing coals show increased diffuseness with decrease in hydrogen content. The diffuseness is accompanied by increase in the uranium content of the coal. It is very likely that high uranium-bearing coals have predominantly tetrahedral structures.

Jan 1, 1968

By Ralph W. Marsden

The natural iron ores of the Lake Superior Region in the United States are being replaced by iron-ore concentrates produced from magnetite- or hematite-rich horizons in the Precambrian cherty iron formations. The production of natural ores will soon be less than one-half of the total ore shipped annually. The tonnage of natural ore produced will continue to decline until it is a minor percentage of the ore shipped. The natural ores include (1) soft ore, (2) hard ore, ( 3) conglomerate ore and ( 4) siliceous ore. The soft ores are the important ore type and are sometimes termed "Lake Superior type ore". These ores are in situ deposits of hematite and limonite formed by the leaching of silica and other gangue materials in the iron formations. The leaching is believed to have been done by downward moving surface waters. In deep ore deposits, generally over 1000 feet below the present surface, circulation and leaching action may have been assisted by hydrothermal activity. Hard ore deposits occur on the Vermilion and Marquette ranges where hematite or magnetite has replaced the silica (and possibly some silicates) in cherty iron formation. These ores commonly occur in structural situations favorable for the movement of hydrothermal waters. The ores are believed to be the result of hydrothermal action with iron, possibly from the iron formation, transported by hydrothermal waters to areas favorable for the replacement of silica by iron oxides. Certain stratigraphic horizons of the Lake Superior Precambrian cherty iron formations contain sufficient iron as magnetite or hematite, with a grain size and texture that will give adequate mineral liberation, to yield an ore-quality product after grinding and concentration. The magnetite-rich deposits are termed magnetite taconites. These ores occur on the Mesabi, Gogebic, and Marquette ranges. Magnetite taconite ores are unenriched cherty iron formation and are the result of the sedimentary deposition of the iron formation and the metamorphic history of the rock. The commercial quality hematite-rich iron formations in Michigan are termed jasper ores. The jasper ores are being mined on the Marquette and Menominee ranges. These ores are composed of specular or granular hematite associated with quartz and iron silicates. The jasper ores appear to be recrystallized iron formations in which iron, prior to recrystallization, occurred as hematite.

Jan 1, 1968

By George Krauss, Seth R. Thomas

One complete cycle, allstenite to martensite to aus-tenite, of Martensitic transformation was induced in a commercial 18 Cr-8 Ni stainless steel. Transmission electron microscopy showed that the reverse transfarmation, martensite to austenite, perpetuated the dense defect substructure of the martensite produced by the direct transformation, austenite to &apos;martensite, and reproduced the retained austenite matrix orientation. A general precipitation of lathlike M,,C, particles was noted to be present in, and is suggested as cause for, regions of martensite that Izad formed after a complete cycle of transformation. The habit plane of the precipitate particles was found to be within 5 a plane previously established as the habit of nitride precipitates of similar morphology in bcc iron. The direct transformation of austenite (y) to martensite (a) in metastable 300 series stainless steels has received considerable attention in the past,&apos;-8 and the martensite product given special emphasis in recent years,9"*u but little information has been published about the reverse martensitic transformation during which bcc a martensite is converted to fcc y austenite."-" The reversal mechanism and the resulting crystallographic relationship between parent and product austenite are of fundamental concern. The reversal product, fully austenitic, and hereafter referred to as reversed austenite, exhibits a defect structure far different from its virgin counterpart. Some studies have been reported in which the structure of reversed austenite in iron nickel alloys is compared to annealed austenite with respect to austenite strengtheningM and Stabilization.&apos; The martensite in these Fe-Ni alloys, however, shows a basic difference from that produced in stainless steels. Structurally, the Fe-Ni martensite is profusely twinned," while the (low-carbon) Fe-Cr-Ni martensite contains a high density of tangled dislocations and is apparently twin-free.I0 reediis" has recently shown in an Fe-16 Cr-12 Ni stainless alloy that this typical martensitic defect structure and the reverse transformation directly influence the structure of the reversal product. He found that much of the reversed austenite had returned to the orientation of the virgin austenite and that fine twins were formed in the austenite after the reverse transformation. This investigation was undertaken in order to describe as completely as possible the structural changes produced by a cycle of transformation in a typical 18-8 stainless steel. EXPERIMENTAL PROCEDURE The 301 stainless steel under investigation (17.44 Cr, 7.75 Ni, 0.80 Mn, 0.60 Si, 0.40 Mo, 0.40 Cu, 0.08 C, 0.03 N, bal Fe)was received as 0.060-in.-thick

Jan 1, 1968