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By P. S. Rudman

Crystal-structure occurrences in binary phase diagrams of fifth- and sixth-period elements, zirconium through palladium and hafniun through platinum, are surveyed with the conclusion that average .group number GN is the dominant correlative. This is interpreted in terms of curves of enthalpy differences between competitiue structures that are continuous func -tions of GN. It is further reasoned that the absolute formation energies may also be continuous functions of GN and if so can be simply obtained from the regatives of the heats of sublimation of the elements. It is shown that from such a heat of formation-GN plot the heats of mixing of alloy systems can be quantitatively predicted. For example, for sixth-period alloys very large exothermic heats of mixing are predicted for systems that span GN = 6 (i.e., Hf-Pt, Ta-Os, ...). Thermodynamic data with which to test these predictions do not appear to be available. If in the latter transition (A subgroup) elements we eliminate from consideration the fourth period where magnetic terms contribute to crystal-structure stability, as shown in Table I, there is a very regular sequence of structures. Using the group number (GN) assignments of Table I, which differ from the usual assignments of 8 to the elements listed as 8 through 10, it is perhaps trivial to say that the phase occurrence is a unique function of GN. However, the interesting aspect of alloys from among these elements is that the alloy structures also appear to correlate with GN. The GN for an alloy is given as GN = SixiGNi, where xi and GNi = atomic fraction and GN of component i, respectively. It is difficult to credit anyone in particular with having discovered this correlation, so many people have implicitly or explicitly employed it in the last 10 years. However, Bloom and Grant' in their correlation of s-phase occurrence with total number of d + s electrons were certainly one of the first to appreciate the correlation and Hume -Rothery2 appears to be responsible for the use of average GN as defined above. Only in the last few years have the phase diagrams of enough alloy systems been determined for this correlation to be surveyed with any degree of completeness. We shall here, in an abbreviated format, summarize the available phase-diagram literature and discuss some consequences of the GN correlation. BINARY DIAGRAM SURVEY In Figs. 1 to 3 the phase occurrences are summarized. In Fig. 4 the occurrence limits for the more common structures are summarized. That the GN of an alloy falls within the occurrence limits of a particular structure is a necessary but not a sufficient condition for the appearance of that structure. The preceding figures certainly illustrate that GN is a dominant correlative for structures of these elements. Many of the diagrams have complications, with ordering and other phase changes occurring in intermediate phases, that cannot be clearly accommodated in such a schematic survey and have hence been left out. Such omissions cannot, however, negate the GN correlations discussed here. Relative atomic size is also an important crystal-structure determinant and since atomic size varies quite regularly with GN for these elements it is possible that the apparent GN correlation is basically a size correlation. In Fig. 5 relative size occurrence limits are given for intermediate phases and extended terminal solutions. The relative volume, ?v/(v) - 2(vA - vB)/(vA + uB), has been taken as the measure

Jan 1, 1968

By Peter Hood

Data on world-wide geophysical activity in mining exploration programs are collected annually by the Society of Exploration Geophysicists' Geo-physical Activity Committee as part of a continuing service to the industry. The data are obtained by sending out questionnaires to all organizations which are known to be carrying out mining geophysical work; the organizations canvassed include mining companies, contractors, government departments and universities. The questionnaire is divided into three sections; namely, ground methods, airborne methods and research. The data compiled from the questionnaires show that world-wide utilization of mining geophysical methods reached a new high in 1967 with total expenditures of (U .S.) $32,323,240. This was divided as follows: ground methods, $18,106,785; airborne methods, $10,-123,405; and research, $4,093,050. For the ground methods, most money was spent on the induced polarization technique ($5,681,780); electromagne-tic methods were second in reported expenditures ($2,010,900). The total reported geophysical line mileage flown was 1,275,072 line miles, with aeromagnetic surveying being the most popular airborne method. The total amount spent on aeromagnetic surveys was $5,832,564 for 895,420 line miles. This gives an average cost of (U.S.)$6.50 per line mile.

Jan 1, 1968

By Joseph W. Martin

The Bureau of Mines investigated the backscattering of low-energy gamma rays as a method for rapidly determining the incombustible content of coal mine dust. In this method, 60-kev gamma rays from americium-24l penetrate the dust and are reflected by elements in the dust to a thin crystal scintillation detector. The number of backscattered gamma rays is proportional to the incombustible content. Tests of 40 dry, mine-dust samples containing 50 to 100 percent inert material show an average error of 2 percent. Calibration of the apparatus is necessary for each rock dust to account for variable composition. Results for samples containing more than 6 percent moisture are subject to error, but the values are lower than values obtained by chemical analysis, and thus fall on the safe side. Development of a small portable meter based on the backscatter principle appears feasible. Such a meter would find application within coal mines to check the effectiveness of rock dusting procedures.

Jan 1, 1968

ABSTRACTMechanised cut and fill stoping in the Racecourse orebodies between II and 9 levels was started in 1964.Five stopes are in progress over the two level interval, extracting the full strike length (600-2,000 ft) of each orebody without transverse pillars.Each stope is served by a central 10 ft by 12 ft service intake ventilation raise and an 8 ft by 8 ft return air raise at each end of the stope. Each stope is divided into two sections for drilling. firing. mucking, and fillingto maintain steady production. All equipment is kept in the stope for one level lift stoping. Gardner-Denver 2 boom jumbos are used for uphole drilling and Wagner ST 5 Scooptrams for loading and transport to ore passes located in the footwall of the orebody. A Wagner PTIO is used for materials handling and scaling of the stope backs.Mill tailings, after one stage of cycloning are used to fill the stope, one section at a time. About 80 per cent of the water is removed by decantation while the remainder percolates through hessian-covered pipes and boxes.The ore is passed to 11 level where it is hauled by the 3 ft 6 in. gauge train to the tipple at the shaft area. The ore is crushed underground before hoisting to the surface.A performance of about 100 ton/manshift is achieved by the drilling, blasting, and mucking crews in the stopes.

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 T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,' sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.' The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By Glenn H. Damon

Concern about environmental pollution goes back many centuries, but until recently most efforts to control it have been perfunctory and spasmodic, aimed largely at coal smoke and other visible pollutants. Air pollution is to a large degree a byproduct of our economic development, and scientific knowledge of the causes and character of such pollution is more extensive than the technology to handle the waste byproducts of our industrial civilization. The removal of all constituents foreign to the air from the effluents produced by an industrialized society is obviously impractical at this time. There is widespread difference of opinion regarding acceptable ambient air concentration levels for the Various pollutants produced by combustion processes, but there is basic agreement that the pollution of the atmosphere must be controlled and eventually reduced. The magnitude of the air pollution problem has been increasing rapidly because our expanding economy calls for an ever-increasing consumption of energy, and fossil fuels are a principal source of energy. For example, the consumption of electricity has been increasing at an average annual rate of approximately 8 percent over the last 10 or 1.5 years. Table 1 shows the estimated emission of the principal pollutants into the atmosphere in 1966. The approximately 90 million automobiles, trucks, and buses on American highways contribute the largest proportion of pollutants to the atmosphere, but that fact does not alter the growing problems of the coal industry. You will note that sulfur oxides, particulates, and nitrogen oxides are all products of the combustion of coal. Of these air contaminants, sulfur oxides are now receiving major emphasis in terms of research to develop effective means for control, Table 2 shows that the combustion of coal produces approximately 60 percent of the sulfur oxides discharged to the atmosphere. While the utilization of coal is the principal source of particulate matter, this is not considered as serious a problem as it was in the early part of the century because of technological developments that have produced sound methods for the removal of particulates from waste gas streams.

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

By M. E. Wadsworth, A. S. Peck

Infrared spectra disclose that oleic acid will not adsorb on the surface of pure beryl unless the mineral is first activated with HF. The adsorption of oleic acid on HF activated beryl is attributed to the hydrogen bonding of oleic acid monomers to F-surface bridging sites. These sites are formed as a result of the reaction of HF with chemisorbed water or surface hydroxyl. Characteristic infrared spectra of physically adsorbed oleic acid are correlated with flotation at different pH at temperatures of 25°C and 75°C for colloidal and -60-mesh particles. The usual mode of occurrence of the beryllium mineral beryl, Be3A12Si6O18, is in granite pegmatites as pale green, white, or yellow crystals. A dark green gem variety, emerald, may be found in the wall rock of pegmatite veins or in mica schist. The most important beryl deposits in the United States are in the Black Hills District of South Dakota, and several mountain ranges of central and west-central Utah contain potential commercial sources of this mineral. Several papers have been published concerning the flotation of beryl with different conditioning reagents. Kennedy and O&apos;Meara1 reported on the essential use of HF in the flotation of beryl from different ores. The use of calcium hypochlorite to separate HF activated beryl from feldspar after flotation with an amine collector was made by Runke.2 A report on the activation of beryl with different cations using sodium oleate collector was presented by Viswa-nathan and co-workers.3 Flotation of beryl with sulfonate collector and different activating salts was employed by Fuerstenau and Bhappu.4 The role of the surface charge or zeta potential in the flotation of beryl with different collectors and salts was also extensively investigated.5"7 Previous infrared investigations by the authors8 disclosed that the orthosilicate beryllium mineral, phenacite, reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. Thus, chemisorption is the effective mode of adsorption in the phenacite-oleate acid flotation system. In contrast, neither chemisorption or physical adsorption of oleic acid occur on the surface of pure beryl as evidenced in this study. Efforts were subsequently made to determine the mechanism of activation and collector adsorption for HF pretreated beryl. EXPERIMENTAL PROCEDURES Large, white, terminated crystals of beryl were obtained from Madagascar through Ward&apos;s Co., Monterey, Calif. The crystals were broken into -60-mesh fragments in a porcelain mortar. Part of this prepared material was ground to a powder with a Fisher Grinder using an agate mortar and pestle. The powder was transferred to a graduated cylinder and mixed with 500 ml of distilled water. After 5 min, the colloidal suspension was separated from the settled particles by decantation and used as a stock for infrared test determinations. Adsorption tests were performed by first transferring 20 ml of colloidal suspension to 50 ml glass centrifuge tubes. The solids were then centrifuged out and the liquid was discarded. Then, the solids were pretreated with one molar HC1 or one molar HF. After 15 min, the solids were again centrifuged out. The mineral solids were washed free of residual acid by repeated centrifuging and water washing operations. Then, 20 ml of distilled water was added to the solids, and the resultant suspension was used for test purposes. In the preparation of mineral for flotation tests, 1.5 g of -60-mesh beryl was deslimed by removing the colloidal fraction by three successive water washes and decantations. Then, the coarse particles were pretreated with either one molar HCl or one molar HF for 15 min. The mineral was next washed free of acid with distilled water, and 20 ml of distilled water was added to the beryl prior to collector conditioning. The conditioning of mineral with collector was performed in 50 ml centrifuge tubes to which either NaOH or HC1 was added for pH modification. One drop (6.0 mg) of U.S.P. reagent grade oleic acid or 2 ml of 0.01 molar sodium oleate was added to the pulp and stirred at about 1500 rpm for 3 min at a

Jan 1, 1968

By Frank G. Snyder, Paul E. Gerdemann

The Southeast Missouri lead district, located about 70 miles south of St. Louis, embraces four important sub-districts and several minor ones. The important sub-districts, in order of discovery, are Mine La Motte, the Old Lead Belt, Indian Creek, and the Viburnum Lead Belt. Descriptions that follow are of geology and ore deposits of the Old Lead Belt. The ore deposits are stratiform in character and are localized in a narrow carbonate bar and algal reef environment on the flanks of exposed Precambrian of the St. Francois Mountains. Ore structures include a variety of primary depositional features such as pinchout zones, disconformities, ridge structures, reefs, and submarine gravity slides. Faulting, prior to and during ore deposition, "prepared" the host rock and strongly fractured areas are mineralized much more intensively and extensively than unfractured parts of the same sedimentary structures. The deposits are epigenetic in character. Mineralization is believed to have occurred at the time that post-lower Ordovician faulting took place. The mineralizing solutions are believed to be concentrated brines from adjacent basins that moved out of the basins during faulting, uplift, and erosion of the St. Francois positive area.

Jan 1, 1968

By Samuel M. Brock

Problems related to strip and auger coal mining have grown with the development of the industry and the economy. New technology has produced equipment that has made mining by surface methods not only highly productive, but potentially highly destructive of water resources and natural environments. On the other hand, growth of the economy has produced an increased demand for clean water, and created new demands for amenity values that natural environments provide. Thus, opposing forces have created conflicts in resource use. And these conflicts have made surface mining highly controversial. Resolving the controversy will require the solving of complex economic and social problems. The essence of the economic problem created by surface mining is that, in the absence of proper regulation, substantial costs resulting from the process are borne by the public rather than the mine operator.

Jan 1, 1968

Jan 1, 1968

By Leo J. Vogel, E. D. Hummer

INTRODUCTION by E. D. HUMMER An efficient refuse-disposal system is a necessary part of the modem cleaning plant. The large-scale refuse system and disposal area, engineered for the lifetime of the plant, has become more important due to the greater tonnages of refuse produced from increased quantities of mechanically mined and prepared coal. Laws and increased government regulations have affected the design and operation of disposal systems. THE EFFECT OF MINE AND PLANT OPERATION Refuse disposal starts at the mining face. The mining system, the type of roof support, the machinery used, and the degree of discipline at the face contributes to the amount and type of refuse that must be removed through the disposal system. Economies gained through modification of the mining system or mining machinery may be partially offset by increased dilution of the mined coal with impurities from associated rock formations. In some cases the change in the mining system and equipment has reduced the dilution. In all cases the ratio of impurities that must be removed from the raw-coal feed to the plant not only affects the maintenance and operating costs of the plant, but greatly affects the design of the refuse disposal system. The design of a mine and plant should include the location and the estimated capacity of the disposal areas for the life of the property or plant. Complete evaluation of the disposal system and an estimate of its annual cost of operation over the life of the property or plant should be incorporated in the plant and mine evaluation. Plant design should be as simple as possible, consistent with the efficient production of clean coal. Material transfer points, crushing, screening and pumping operations should be kept to a minimum to reduce degradation and the subsequent increased difficulty and cost of refuse removal. The maintenance of good process control by operating management will result in a minimum of misplaced material in both refuse and clean coal. Reduction of misplaced float material in the plant refuse is an important factor in preventing combustion in the refuse storage pile. THE REFUSE DISPOSAL AREA Combustion in refuse piles occurs when air enters the pile in sufficient quantity to support oxidation. At certain rates of air in-filtration, the heat produced by the oxidation process is not dissipated and temperature rises.

Jan 1, 1968

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

By B. J. Bayles, J. A. Ford, M. J. Salkind

Unidirecltonally sulidijied AL-A13Ni was found to exliibit excellent microstructural stability to 508°C. Above this temperature the transverse micvostructure coarsened in a manner analogous to "Ostwald Ripening", but the A13Ni whiskers did not spheroidize or foreshorlen. The coarsened whiskers reinforced the matrix as effectirely as the finer whiskevs and no reduction in room-temperature tensile strength mas noled after exposure for 90 hr at 96 pel 0-1 the absollite melling temperature of the eulectic. The slability was auribucted to the presence of low-index (and presurrlably lor-energy) cvystallographic interjaces between phases. The driving force for microstructural coursening was presumed to be the reduction of interfacial energy between the phases. Finer micvoslructures were found to coarsen more rapidly than those which weve imitally coarser. FIBER-reinforced metals have been shown to exhibit good short-time tensile properties at elevated temperatures.1-4 However, many elevated-temperature applications require long-time property retention which dictates the necessity for microstructural stability. Two types of instability are common to fiber composities. The first, chemical instability, is due to chemical reaction between the matrix and the relnforcing phase. Petrasek and weeton5 have shown that chemical reaction between tungsten wire and several copper alloy matrices resulted in degradation of the reinforcing phase and reduction in strength of the composite materials. Kreider and Leverant4 have noted similar behavior for boron-reinforced aluminum above 400°C. The second type of instability arises in systems in which the phases are essentially chemically stable with respect to each other and is characterized by spheroidization and/or agglomeration of the reinforcing phase. parratt6 has reported this type of degradation to occur relatively rapidly at moderate temperatures for nickel and cobalt alloys containing whiskers of silicon nitride, aluminum oxide, and silicon carbide and has identified it as "physicochemical" instability. Although both types of instability are the result of the differences in the chemical potential between the fibrous phase and the matrix, they may be differentiated by the fact that the second type, "physicochemi-call&apos; instability, results in little or no net change in the composition or amount of each phase present. It does, however, result in a morphological change which profoundly affects the strengthening mechanism. Chemical interaction. on the other hand, results in a change in the composition and amount of one or more of the phases present, or the appearance of a new phase. In the latter case, the appearance of the mi-crostructure, that of a fibrous phase aligned in a matrix, may remain essentially unchanged, but the chemical degradation of the fiber results in markedly reduced composite strength. This investigation was initiated in an attempt to evaluate the microstructural and related mechanical property changes of a whisker-reinforced eutectic composite after elevated-temperature exposure. The composite system chosen for this study was the uni-directionally solidified A1-A13Ni eutectic which Lemkey. Hertzberg, and Ford7,8 demonstrated to behave as a whisker-reinforced composite. The microstructure of the unidirectionally solidified material consists of aligned needles of A13Ni in a matrix of aluminum. EXPERIMENTAL PROCEDURE Eutectic ingots having a nominal composition of 6.2 wt pct Ni were produced by melting 99.99+ pct A1 and 99.99 pct Ni in recrystallized alumina crucibles in an argon atmosphere. The analyses of the starting materials are listed in Table I. These master heats were cut up? melted by induction heating, and unidirectionally solidified vertically in 1/2 -in.-ID. 6-in.-long graphite crucibles, in a dynamic argon atmosphere. Therma1 gradients in the liquid were determined by measuring the temperature in the melt as a function of apparatus travel distance, as discussed by Kraft and Albright.9 The rate of solidification was assumed to be equal to the uniform rate at which the crucible assembly was withdrawn from the furnace. Ingots representative of nominal growth rates of 2, 5, and 11 cm per hr were produced and the solidification parameters are summarized in Table 11. Ingots used for met allographic analysis were pre-

Jan 1, 1968

By B. K. Asdell

Crude kaolin exhibits a wide particle size range in which kaolinite is the predominant mineral. Bene-ficiation by wet processing produces high-brightness white pigments. The wet processing techniques peculiar to kaolin beneficiation are emphasized in this article in some detail. Included are discussions of long-distance pipeline transportation, centrifuga-tion, flotation, spray drying and shipment as 70% solids slurry. Georgia, a state seldom considered to be an important mineral producer, has one surprising feature — it is the nation&apos;s largest producer of kaolin. Kaolin is a highly important raw material in the paper, rubber, ceramic whiteware, paint and chemical industries. In 1965, more than 2.7 million tons of kaolin were produced in this state, a 150,000-ton increase over the preceding year, and production continues to climb. Strictly defined, the term "kaolin" applies to a group of hydrous aluminum silicates in which kaolinite is the predominant mineral. Kaolinite is inherently white, non-abrasive, chemically inert, and of a very fine particle size, ranging from sub-micron to 40-microns equivalent spherical diameter. An electron-micrograph of kaolinite is shown in Fig. 1. The particles finer than about 2 microns are thin, elongated plates, hexagonal in outline. The larger particles, coarser than 2 microns, are predominantly vermicular in outline with a foliated structure. Table I shows a typical chemical analysis of commercial, wet-processed kaolin compared to pure kaolinite. The sedimentary Cretaceous deposits of the Coastal Plain are the source of most of the kaolin produced in the Southeast. These deposits are of relatively high purity, and it is not uncommon to find the clays running greater than 90% kaolinite. Beneficiating plants using wet processing techniques are most numerous in an area within about 50 miles east of Macon, Ga., in a band approximately 15 miles wide. Kaolin may vary widely in quality from one deposit to another, or within the same deposit. The qualities critically examined are brightness index as measured by reflectance, viscosity of water suspensions, bleachability and particle size distribution. Crude kaolin always contains sand and mica in varying amounts, along with small amounts of many other minerals. These are classed collectively as "grit" because; they are generally coarser than 325

Jan 1, 1968

By Thomas M. Nasiatka

This report briefly describes the present state of the art and the technological highlights of tunneling from its inception to the present. The discussion is concerned primarily with tunnels driven through relatively competent rock for mine development and various civil purposes. In addition to pinpointing the major technological breakthroughs in tunneling, this report indicates their general effect on the speed of tunneling. The tunneling speeds are based upon data from approximately 80 tunnels listed in the appendix. These data include length; cross section shape and dimension; type of rock; tunneling method; method of breaking, loading, and transporting the rock; average linear progress rate; and cost in values during the period of construction. Most of the tunnels described have diameters of 15 to 30 feet.

Jan 1, 1968