Search Documents

By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By G. E. Pellissier, P. H. Salmon Cox, B. G. Reisdorf

Banding that occurred in plates rolled from the early production heats of 18Ni(250) maraging steel is described and related to the segvegation of certain alloying elements (nickel, molybdenum, titanium), the extent of which was quantitatively evaluated by means of electron-microprobe analysis. The effect of banding on mechanical properties is discussed, with particular reference to observed directional differences in plane-strain fracture toughness of plates. It is shown that banding originates as interdendritic segvegation during ingot solidification and persists in some degree through normal soaking and hot reduction to plate. The results of the study showed that heating sections of small laboratory-cast ingots at 2200°F for 4 hr was sufficient to markedly reduce microsegregation and to considerably improve mechanical properties. Hot rolling of 7-in.-thick ingot sections to 1/2-in.-thick plate effected a similar reduction of microsegregation, but resulted in even greater increases in ductility and toughness than that obtained by homogenization treatment alone. DURING the past few years, considerable attention has been directed towards the low-carbon, high-alloy maraging steels and in particular towards the 18Ni-8Co-5Mo-0.4Ti alloy. The steels of this group, having an excellent combination of high strength and toughness, have a number of advantages over their more conventional medium-carbon low-alloy, quenched-and-tempered counterparts. In the annealed condition, the maraging steels are in the form of a ductile marten-site; aging at a relatively low temperature, typically 900°F for 3 hr, increases greatly the strength through the precipitation of intermetallic compounds. One problem in the early production heats of maraging steel was that the finished plate frequently displayed a banded structure. Previous work on other steels1-' had established that banding in wrought products is either a direct or an indirect consequence of chemical segregation, which occurs during solidification and persists to some extent through normal thermal and mechanical treatments. For example, Smith and others: in a study of low-alloy steel, were able to correlate the severity of banding in the wrought product with the degree of interdendritic segregation of nickel and chromium in the as-cast ingot. The effect of banding on the mechanical properties of steels is usually considered to be detrimental, although there is only limited evidence to suggest that a marked improvement in properties can be obtained with less heterogeneous structures. Comparison of the longitudinal and transverse tensile properties of banded and of homogenized 4340 steel showed that only the transverse ductility was improved by homogenization, but even then the improvement was not commercially significant.' Conversely, homogenization of through-the-thickness tension specimens of quenched-and-tempered steel plate, containing 1.47 pct Mn, increased the strength by as much as 10 pct and the tensile ductility by at least a factor of twos5 This improvement was related to the elimination of manganese-rich bands, which also are one of the factors responsible for cold cracking in the heat-affected zone of metal-arc welds.7 In the present study the nature and severity of banding in early commercial 18Ni(250) maraging steel plate and in laboratory-melted 18Ni(250) maraging steel plate was determined. The effects of banding on plane-strain fracture toughness and the effects of thermal homogenization treatments on the strength, tensile ductility, and toughness of 18Ni(250) maraging-steel as-cast ingots and rolled plate were evaluated. In addition, the effects of hot deformation by rolling on the mechanical properties of ingots were determined. 1) STUDIES OF BANDING IN EARLY PRODUCTION PLATE The chemical composition of the steel (A) used in this part of the investigation is shown in Table I. Banding was not clearly evident in either as-rolled or annealed* plate, but annealed and agedc** plate had a banded structure. The typical banded condition, Fig. 1, consists of layers of unetched austenite (white) and dark-etching martensite in a light-etching martensitic matrix. X-ray diffraction measurements showed that this steel contained more than 6 pct austenite. An electron-probe X-ray microanalyzer (using a focused beam of electrons) was used to determine the composition of the bands and of the material between the bands with respect to the main alloying elements— nickel, molybdenum, titanium, and cobalt. The recorded X-ray intensities were converted to concentration values with the use of a standard of similar composition. To facilitate probe positioning, all analyses were conducted on specimens that had been given a light etch. The influence of this etching on the analytical results was negligible; analyses made on the identical area before and after etching yielded essentially the same concentration values. The results of the electron-microprobe analyses at selected points revealed that the layers of austenite and adjacent dark-etching martensite contained greater amounts of nickel, molybdenum, and titanium than did the surrounding matrix, Table 11. The austenite layers

Jan 1, 1968

By M. D. Banus, M. B. Bever, A. K. Jena

Measurements of the heat effects on addition of various solid phases of InSb to a solution calorimeter have confirmed the existence of a new high-pressure plzase InSbQII), which was jormed at 37 kbar and 623°K. The heats of formation of InSbQ), InSbfl), and InSb(111) have been measured and the heats of transjormation of InSb(1) to InSb(1l) and InSb(Iii) and of 'InSb(ll) to InSb(iiI) at atmospheric pressure and 78°K have been determined independently. Other thermodynamic properties of these phases, the phase boundary InSb(i)/InSb(ll), and the relative positions of the triple points are calculated. The pressure-Dolume term is shown to be more critical than the internal energy difference in making the phase InSbQ) less stable than InSb(II) at high pressures. Observations on partially transformed specimens suggest that the transformation of' metastable InSb (III) takes place in the two steps InSb(lll) — InSbQI) and InSbQI) — InSb(l). The compound InSb can exist as several phases depending on the temperature and pressure. The phase InSb(I), which is a semiconductor having the zinc-blende structure, transforms into the phase InSb(11) at a pressure of about 23 kbar and room temperature.'-3 The phase InSb(II) has the 6 tin structure,4-6 is metallic, and becomes a superconductor below 2.lok7 An orthorhombic phase of InSb has been reported to occur above a pressure of approximately 30 kbar at room temperature.' This phase is also a superconductor below about 3.4k9 The phase InSb(I1) is retained at atmospheric pressure if it is quenched to 78°K under pressure,6,7 but tends to transform at higher temperatures and does so explosively above approximately 210ok,7 A value of the heat of transformation of InSb(1) to InSb(II) at 210°K and atmospheric pressure has been reported.' A concurrent publication'0 reports evidence for a new solid phase InSb(III), which was formed by annealing InSb above 58 1°K at 37 kbar, above 560°K at 52 kbar, and above 473°K at 65 kbar. Specimens of InSb(II1) had a superconducting transition temperature of 4.lo ± 0.1oK. X-ray diffraction patterns also indicated the presence of a new phase. In this communication, thermodynamic properties of the phases InSb(I), InSb(II), and InSb(II1) are reported and discussed. The phase boundary InSb(I)/InSb(II) and the relative positions of the triple points are calculated. 1) EXPERIMENTAL 1.1) Preparation of Specimens. Specimens of the high-pressure phases of InSb were prepared in a belt-type high-pressure chamber by a tichnique described in detail elsewhere.'' Charges of 0.6 to 0.8 g of Cominco semiconductor grade InSb were used. The temperatures were measured with a chromel-alumel thermocouple, the hot junction of which was within 0.5 mm of the specimen. The specimens were heated under a pressure of 37 kbar for 1 hr at 723°K (which is well above the liquidus) and quenched to room temperature. One set was annealed at 523°K and another set at 623°K for 20 to 24 hr. These annealing temperatures were chosen because 523°K was below and 623°K was above the temperature of the transformation of InSb(II) to InSb(1Tl) at 37 kbar.10 The specimens were then cooled to 125°K by passing liquid nitrogen through the jacket of the belt die before the

Jan 1, 1968

By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year's duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10' dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors' Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By D. M. Boulin, E. S. Greiner

Single crystals of vanadium were bent at 293" and 77°K to a maximum fiber strain of about 1 pct. Analysis of slip line and etch markings of- crystals deformed at either temperature show the slip planes are {112}. The slip directions at 298° and 77°K, deterwined from the asterism axes of rotation of crystals compressed in a {110} direclion, were (111). Etch pits, associated with dislocations, were observed in the plastically deformed vanadium. There was no evidence of mechanical twinning. THIS paper presents results on single crystals of vanadium plastically deformed by bending and compressing at 298° and 77°K. Bcc metals have been observed to slip on {110}, (1121, and (123) planes while the slip direction has invariably been found to be ( 111) 1 Lindley and smallman2 have studied the deformation intension of polycrystalline vanadium between 298° and 20°K and reported that at and above 77°K the deformation is predominantly by slip, but at 20°K the deformation is associated with twinning. Later, Edington and smallman3 found that single crystals of vanadium compressed in a (111) direction at 77°K deformed by twinning on { 112}( 111) systems. Clough and pavlovic4 have reported that mechanical twins were observed in vanadium loaded by impact at 77°, 173°, and 195°K, respectively. PREPARATION OF SINGLE CRYSTALS The vanadium single crystals were made from commercial vanadium reported to contain 0.03 pct C, 0.03 pct 0, 0.02 pct N, 0.0X* pct Ca, 0.0X pct Si, proximately 0.8 cm diam, 4 cm long and were grown in (100) and (110) directions. A crystal for studies of etch pits was gound to have a face parallel to a {l00} plane by the Bond crystal-orienting technique.7 In order to avoid straining, the crystals were placed on the steel mount with a low-melting organic compound (glycol phthalate) before grinding. Crystals for the bending experiments were ground to have the four side faces parallel to ( 100) planes. The crystals were electropolished8 in 10 pct H2So4 using a current density of about 3 amp per sq cm to remove the strained surface material. The crystals were bent slowly by three-point loading in a stainless-steel jig designed by Sylwestrowicz.9 The end rollers of the jig were 3.8 cm apart. DEFORMATION AT 298°K The bent vanadium crystal, after removal from the jig, had a radius of curvature of 20.4 cm over the 2-cm length close to the center loading roller, where the maximum bending moment occurred. This radius of curvature corresponded to a maximum fiber strain of 0.9 pet. The side faces contained slip bands as shown in Fig. 1. These bands are straight where the strain is high, top and bottom of micrograph, but are curved on either side of the neutral axis in the center. This curvature of the slip bands in the low-stress area may be due to cross slip. The plastically deformed crystal was subsequently electropolished and then electroetched in 10 pct H2SO4 solution, using a current density of 0.25 amp per sq cm. The structure is shown in Fig. 2. The directions of the traces on two adjoining faces were plotted stereo graphically, Fig. 3.* Since there were two sets of

Jan 1, 1968

By R. Kossowsky

Structural changes in Be-Cu, Be-Ni. Be - Ag, and Be-Fc alloys pressurized in a solid medium were invesligated by resistivity measurements , X-ray diffrac lion in situ and metallogvaphic examination. Some limited tests in liquid medium were also conducted. Good correlation was oblained between diauges of slope of relative resistance us pressure and changes in diffraction pattern. Metallographic examination rez:ealed that the copper, silver, and nickel alloys lwiu heauily due to the applicalion of pressure at room temperature. Using polarized light technique {1012}, {1011}, and possible {1010} twinning planes were identified. At eleuated temperature twinning was moslly confined to the {1012} planes. Although twin-ning could be promoted by application of hydroslutic pvessure (liquid medium), it was strongly enhanced by the pvesence of a nonhydvostatic shear component due to pressurizalion in a solid medium. It was further obserced that a decrease in grain size inlnibiled twinnitzg activily. A great deal of effort has been expended in recent years to render beryllium useful for structural applications. Efforts were concentrated towards a possible phase change and to promoting other than basal deformation modes. Quenching experiments to obtain the high-temperature bcc phase have failed,' nor were alloying additions successful in improving ductility of the brittle hcp phase.2 Herman et a1.3 have reported a new {1011} twinning mode in a Be-4.4 wt pct Cu alloy oriented for a C axis compression sustaining loads to 440,000 psi. A new approach using high-pressure techniques was undertaken at Curtiss-Wright, Wright Aeronautical Division Laboratories. Marder4 reported a 25 pct decrease in relative resistance of commercially pure beryllium at 92 kbar. He proposed that this discontinuity corresponded to the bcc phase found at high temperature; however, X-ray diffraction in silu did not confirm a phase transition.5 contre6 has recently shown that the bcc transition in pure beryllium is lowered to 800°C at 80 kbar accompanied by a 50 pct increase in relative resistance. The purpose of this paper is to report on one phase of an investigation of the effects of high pressures and temperatures in beryllium alloys, namely, twinning behavior in Be-Ni, Be-Cu, Be-Fe, and Be-Ag alloys pressurized to nearly 100 kbar and temperatures up to 200°C. EXPERIMENTAL METHODS Material was obtained from Nuclear Metals, Inc., in the form of a 1.5-mm-diam wire extruded in stainless-steel cladding at 1600° F. Nominal composition of the alloys is listed in Table I, and the major impurities are are given in Table 11. Pressures to 100 kbar* were ob- tained using a National Bureau of Standards type 100/400 ton tetrahedral unit supplied by Barogenics, Inc. This type of apparatus contains a retaining sleeve with a conically tapered internal surface and four pressure-intensifying anvil assemblies with tungsten carbide tips. The 10-mm-long specimen fits into a pyro-

Jan 1, 1968

By David B. Brooks

Identified potential resources of lead and zinc are lower, relative to reserves, than the same ratio for other metals, Either there is little material below present grades or, if it exists, there are no data on it. The author examines both these factors in detail, and also introduces a third possibility. In their 1961 monograph, The Future Supply of the Major Metals, Bruce Netschert and Hans Landsberg noted that identified potential resources (that is, known but submarginal resources) of lead and zinc were much lower relative to reserves (that is, known and supermarginal resources) than was the same ratio for other metals.' Put another way, it seemed that for such metals as iron, manganese, copper, and aluminum, slightly more favorable economic conditions or modest advances in technology would greatly increase reserves by permitting the exploitation of vast quantities of leaner or deeper or otherwise less valuable mineral deposits. But for lead and zinc, Netschert and Landsberg concluded that either: "(1) there is relatively little material below present cutoff grades; [or] (2) such material exists, but for some reason there are no data.'12 This situation, which they called "the lead-zinc anomaly'' has been subsequently discussed by other authors. The purpose of this paper is to carry the discussion further by examining the evidence in favor of (1) and (2) and by advancing a third alternative. There are at least two reasons for devoting time to the lead-zinc anomaly. First, while it is unlikely that we shall have to turn to alternative lead or zinc resources in the near or middle-term future, the longer run resource picture for the two metals is not so certain.3 Both within the United States and for the world as a whole, new discoveries will have to come at a fair pace to keep up with growing rates of consumption. Thus, it is important to see whether there exist lower grade or nonconventional potential sources of two such useful metals that we could turn to at some time in the future. The second reason for studying the lead-zinc anomaly is also related to resource adequacy, but is of more general significance. Depending upon whether the anomaly is technologic, geochemical, spatial, or temporal in origin, we shall be able to draw some conclusions about the resource picture for other metals. Can we expect the apparent pattern of lead-zinc resources to be repeated? If so, will technologic advances in either exploration methods or mineral processing be able to alter the pattern? Or is the pattern unalterably set by geochemical distribution? Most important, are metals characterized by what seems to be an anomaly, different in any way from metals for which low-grade or nonconventional sources already have come to be exploited, as the porphyry deposits have for copper. In sum, investigation of the lead-zinc anomaly represents a case study combining both physical and economic aspects that may open up a neglected area in evaluating mineral resource adequacy. WHAT IS THE LEALLZINC ANOMALY? There are two dimensions to evaluations of the potential of any mineral resource? The first involves the degree of certainty that we ascribe to the estimate: how much do we know about the size of the resource as a result of geological mapping, exploration, and mine development? This dimension is expressed by the terms measured, indicated, and inferred reserves (and, if you wish, 'undiscovered reserves'), all of which terms carry with them the implication of exploitability under current cost-price conditions. The other dimension to evaluations of a mineral resource involves the economic limits of the estimate: how will the size of the resource vary with different (usually more favorable) cost-price conditions? (This economic dimension should be understood broadly to include all factors bearing on the cost-price relationship. In this sense it subsumes technology because any resource is exploitable at some cost; the role of technology is to bring cost down.) The latter dimension is expressed in the terms potential or sub-marginal 'ore,' and is logically quite independent of the former. For example, we have relatively good measurements of the tonnage of manganese in low-grade deposits in this country, though they are too lean to be considered reserves; on the other hand, we are much less certain of our measurements of new lead and zinc deposits in Missouri, though there is no question but that there is a sizable reserve. Thus, it may be uncommon but is not a contradiction to talk of measured submarginal ore or inferred potential ore.

Jan 1, 1968

By H. C. Fiedler

The solubility of sulfur in Si-Fe was determined by the metallographic examination of heat-treated and quenched samples. In the absence of manganese, the solubility in 3.1 pct Si-Fe was found to be about 0.010 pct at 1000o C, 0.015 pct at 11000C, and 0.020 pct at 1150°C, which is substatntially less than hitherto reported. Increasing the silicon content was found to decrease the solubility of sulfur, which is consistent with the increase in the activity coefficient of sulfur with increasing silicon content that has been reported for Fe-Si alloys. Manganese additions were studied in alloys containing 3.1 pct Si and between 0.013 and 0.015 pct S. At low manganese levels the solubility product of manganese sulfide was found to be lower than previously reported. THE solubility of sulfur in pure polycrystalline iron has been reported by Rosenquist and Dunicz1 and by Turkdogan et al.2 Samples were equilibrated in atmospheres containing different ratios of H2S/H2. Both groups of investigators found a solubility limit in y iron of 0.013 pct at 1000oC and 0.031 pct at 1200°C. In addition, Rosenquist and Dunicz1 found a solubility limit in a iron of 0.020 pct at 900°C. Ainslie, Hoffman, and seybolt3 found significantly higher sulfur contents in polycrystalline iron samples than in single-crystal samples after heating at 890°C in a sealed tube containing a mixture of powdered iron and FeS made with s35. Whereas the single crystals contained 0.013 and 0.016 pct S (± 0.005 pct), the polycrystalline samples contained between 0.016 and 0.026 pct S. Autoradiographs suggested that the excess sulfur in the polycrystalline samples was due to the segregation of sulfur in solution at grain boundaries. Ainslie and seybolt4 have reported on the solubility of sulfur in 3 pct Si-Fe. Their samples were sealed in capsules containing hydrogen and sufficient sulfur as cobalt sulfide to saturate the sample. After heat treating, the sulfur-rich phase on the surface was removed by abrading, and the sulfur content of the sample was taken as the equilibrium value for that temperature. Before the equilibrating heat treatment, the samples were heated to 1300°C to coarsen the grains. The resulting grain size, which was about 3/18 in. in diam, was considered sufficiently large to preclude a sensible increase in sulfur solubility due to grain boundary segregation. They reported the solubility to be 0.029 pct at 900oC, 0.063 pct at 1000oC, 0.076 pct at 1100°C, 0.122 pct at 1200°C, and 0.098 pct at 1300°C.

Jan 1, 1968

By I. S. Levy, J. L. Brimhall, B. Mastel

Specimens of' Hastelloy X-280, a low-cobalt version of the solid-solution- hardened nickel-base alloy Hastelloy X, were given a series of thermomechanical treatttzents. They were then Lensile-tested at room temperature and 1350°F. The Microstructures of the specimens tested at 1350°F were studied by electron Microscopy. Microscopy showed that dislocation tangling, caused by the cold working, mas still in evidence after aging-for 24 hr to temperatures as high as 1550oF. (Cr, Mo)23 C6, (Fe, Mo)6 C'. as well us an unidentifiable phase precipitale due to the combination of the thermomechanical treatments and subsequent tensile strain. The room -temperature and 1350°F tensile properties show a general increase ill strength and decreccse in ductility with increusing cold-work level. This is due to the dislocation taangling-. PerLurbatiot~s to this general trend occur- due to solid-solution weakening at the higher cold-work levels as a direct result of the preciplitation reactions. THE requirements for corrosion resistance and high-temperature strength place nickel-base alloys among the more promising materials for advanced nuclear reactor applications. However, when these alloys are irradiated at service temperatures, they generally suffer severe embrittlement'" and reduction in rupture life.3 Certain experimental treatments resulted in improvements in the tensile and stress-rupture properties of Hastelloy X-280, a solution-hardened nickel-base alloy.' To provide a basis for understanding these improvements, unirradiated tensile specimens were examined by electron microscopy. The results are reported in this paper. EXPERIMENTAL DETAILS Material. Hastelloy X-280, a low-cobalt version of Hastelloy X, is a member of the solution-hardened class of nickel-base alloys. The Hastelloy X-280 was obtained from 4- and 1-in: thick plates in the mill -annealed condition. Table I gives the chemical composition of the material as reported by the National Spectrographic Laboratories. ~x~erimental Treatments. Plates of suitable size, 12 by 3 by 1 in., or by + in., were cut under a water jet from the stock material and examined ultrasonic -ally for homogeneity of grain size and absence of voids. The acceptable plates were solution-treated at 2150°Ffor 1 hr and air-cooled. These plates were then reduced in thickness by cold rolling 0, 10, 15: or 20 pct along the original rolling direction. The plates were machined into buttonhead tensile specimens with a gage diameter of 0.125 in., with a gage length of 1.125 in., and with their tensile axes parallel to the rolling direction. The specimens were examined for quality of finish with a penetrant dye, ultra son ically checked for voids, and finally given a dimensional tolerance check with an optical comparator. The acceptable specimens were aged for 24 hr at either 1000" or 1500 F and air-cooled. These specimens were then held at 540°F in a water loop for approximately 18 days to qualify as controls for similar specimens irradiated under the same conditions of time, temperature, water chemistry, and flow rate. Table U summarizes the treatments. These treatments were investigated to establish whether prior precipitation and stabilization of carbide phases at strain sites within the matrix could reduce the amount of carbides available for precipitation at grain boundaries during service. Tensile-Test Conditions. Specimens were tested to fracture at room temperature or 1350 F in air on an Instron tensile-testing machine at a crosshead speed of 0.05 in. per min. The time for the furnace to reach equilibrium at 1350°F was approximately 30 min; soak time prior to testing was 15 min; and test duration was approximately 5 min.

Jan 1, 1968

By S. J. Aresco, George E. Keller, J. Visman

INTRODUCTION The accurate sampling of coal, as with most minerals, is a difficult task. Coal is a very heterogeneous material made up of different types of coal and varying amounts of mineral matter. The product as mined may contain all of the layers of coal and impurities found in the seam as well as portions of the strata above and below the coal seam. The preparation plant is the device to size, crush and/or remove impurities so that the coal may be shipped as a saleable product. Sampling may be needed at many stages in the preparation process. Although this chapter is mainly concerned with sampling in connection with preparation processes, the principles will apply to all coal sampling. The main reasons for sampling in connection with coal preparation are: 1. To determine the washability characteristics of the raw coal by means of float and sink tests. These may be used for the design of a preparation plant, prediction of results to be obtained or for monitoring raw coal delivered to the plant. 2. To check the performance of various operating units in the plant, either by float and sink tests or chemical analyses. 3. To determine the analytical characteristics of the products produced, such as moisture, ash, Btu, sulfur, etc. HISTORY The earliest accepted methods of sampling coal in the United States were given in U. S. Bureau of Mines publications by J. A. Holmes,1 G. S. Pope2 and A. C. Fieldner.3 The American Society for Testing and Materials more or less adopted the methods proposed by the U.S. Bureau of Mines in their Standard D-21-1916, and it remained a standard for many years. Briefly, the standard called for a 500 pound sample for coals less than. 3/4 -in. in size and a 1,000 pound sample for all coals over ?4 -in. in size. No mention was made of increments but there was an instruction that the sample should spread over the coal to be sampled. Sample preparation was by hand crushing with the alternate shovel method for reduction to 250 pounds followed by coning and quartering below 250 pounds. Obviously, with the amount of work involved, this method of sample preparation was rarely followed. This method of preparation resulted in samples that were practically air dried because of long exposure while crushing, shoveling and quartering. In the late nineteen twenties and early nineteen thirties, studies for more practical methods were begun. Dr. E. S. Grummell4, Imperial Chemical Industries, Ltd, London, summarized the work to date at the

Jan 1, 1968

By D. D. Pollock

Many constitution diagrams do not indicate the limits oJ solid solubility of the silver-rich solid solutions below 200°C. Thermoelectric measurements were employed to determine this limit in the nieighborhood of room temperature. The appearance of a second phase causes a discontinuity to occur in the tkevtrroelectric power as a function of cornposition at constant temperature and pressure. This discontinuity was employed to determine the limits of the silver-rich terzinal solid solutions of the Ag-A l, Ag-As, Ag- Bi, Ag--Ge, Ag-In, Ag-Pb, Ag-Sb, and Ag-Sn systenls at 30°C. CONSIDERABLE work has been done on the constitution of binary alloys of silver. The available data have been compiled by Hansen1 and Elliott.2 However, many of the binary diagrams do not show the limits of solid solubility of the silver-rich solutions below about 200° C. This work was undertaken in an attempt to extend these limits to the neighborhood of room temperature . PREPARATION OF ALLOYS All of the alloys were made with silver containing less than 0.014 pct (by weight) of impurities. The materials were weighed out into 225-g heats and melted in a high-frequency induction furnace. The indium, tin, and antimony alloys were melted in A1203 crucibles, under a boric anhydride cover, and were poured into split graphite finger molds. The aluminum, germanium, arsenic, lead, and bismuth alloys were melted in machined graphite crucibles; they were also covered with boric anhydride and poured into split graphite finger molds. The $-in.-diam ingots were heated to 750°C and were forged and hot-rolled down to 0.1 by 0.1 in. The wires were pickled in a 25 pct HNO3-75 pct H2O solution to remove any oxygen-rich surfaces. The wires were then annealed at 550°C for 2 hr in a dissociated ammonia atmosphere. They were then furnace-cooled for 20 hr to room temperature in this atmosphere. The wires were cold-drawn to 0.0808 in. diam. The finished wires were again annealed at 550°C in the same manner as in the first anneal. Thermoelectric Power. The thermoelectric power of a single specimen of each alloy was determined against pure silver which contained a maximum impurity content of 0.014 pct by weight. The wire specimens were straightened and then cleaned with ethyl alcohol. They were then reannealed in the same way as the finished wires to assure that any residual stress would be at a minimum level. Previous work has shown that the presence of small amounts of stress has the effect of decreasing the thermoelectric power. The alloy specimen was soldered to the pure silver wire to form the measuring junction. A standard set of copper leads was then soldered to the reference junctions of the thermocouple. These junctions were maintained in separate dewar flasks which contained finely shaved melting ice during the test. The thermal electromotive forces of the thermocouples were measured at four temperatures between 15° and 45°C. A known source of electromotive force was balanced against the output of the thermocouple until a null balance was reached. The data were then expressed in terms of the thermoelectric power at 30°C. The results were then converted to absolute thermoelectric power, s303.3 These data have an average error of less than ±0.2 pct. RESULTS AND DISCUSSION All of the experimental data are given in Table 11. Since the electromotive forces of the binary alloys of silver were determined against the pure silver from which they were made, the resultant thermoelectric powers are only a function of the intentionally added binary elements at the constant test temperatures. This provides a direct measure of the effects of the alloying elements. The absolute thermoelectric power of an alloy of silver is given4 by:

Jan 1, 1968

By E. J. Efsic, C. M. Wayman

The fcc to bcc y to a transformation in an Fe-24.5 at. pct Pt alloy was studied and found to be martensitic. Large martensite plates are formed in this alloy which are ideal for crystallographic studies; the Ms temperature is about -5°C. Ordering of the parent phase prior to transformation to martensite causes a pronounced lowering of the Ms temperature. For the first time in the case of alloys of iron, measurements of the habit plune, orientation relationship, and magnitude and direction of the shape stvain have been obtained on preselected martensite plates. It is shown that by measuring the initial and displaced (as a result of the shape strain) positions of three or more non-parallel fiducial scratches on one reference surfice the maguitude and direction of the shape strain and the state of distovtion at the parent-mavtensite interface can be determined with a reasonable degree of accuvacy. The agreement between the phenomenolog-cal crystallographic theory of martensitic transformations and the experimental results habit plune, orientation relationship, and nlagnitude and direction of the shape strain) is essentially perfect, and is thought to be the best reported to date for iron alloys. THE comparatively few investigations on binary Fe-Pt alloys have been concerned with magnetic properties, ordered phases, and the equilibrium diagram itself. Various investigations have shown that the equilibrium diagram is of the open y field type; in addition there is a peritectic transformation, a minimum melting point, and three ordered phases: Fe3Pt, FePt, and FePt3. The results of a number of investigators1-6 have shown that the temperature dependence of the y to a (and reverse) transformation in iron-rich alloys is reasonably well-established. The Fe3Pt phase was first noted by Kussman and Rittberg,7 and its existence was later confirmed by Franklin et al,8 Steijn and Donahoe,9 and Berkowitz et al.10 The FePt phase was reported by Isaac and amman' and later confirmed by a host of others.3,6,7,12,13 Kussman and Rittberg7 noted the existence of the superlattice FePt3. Prior to 1956, the 1 to a transformation in iron-rich Fe-Pt alloys was termed "irreversible". In 1957 Klokholm and Donahoe" termed this transformation martensitic, presumably because of its occurrence at temperatures well below those where diffusion normally takes place. This observation served as a point of departure for the present investigation, and in the very early stages of the work to be discussed it was readily verified that the y to a transformation in iron-rich Fe-Pt alloys is indeed martensitic. Quite large martensite plates exhibiting the well-known surface tilt were observed. These plates are ideal in the sense that the boundaries between the parent and product phases were usually very straight. It thus appeared that Fe-Pt martensites would be ideal for crystallographic studies, and this was the purpose of the present investigation. Details of the crystallography of martensitic transformations (particularly for iron alloys) and the phe-nomenological crystallographic theories15-l7 have been discussed many times and thus will require very little elaboration here. The end result of these theories, given in matrix form, is

Jan 1, 1968

By Olin M. Hart

Uranium ores occur in the Lower Cretaceous Inyan Kara group of heterogeneously stratified fluvial and fluvial-marine sandstones in the Black Hills of western South Dakota and northeastern Wyoming. There are three principal mining districts, each in the ancestral and present drainage area of a major river partially responsible for stripping the region to its present topographic form. Primary minerals in the deposits are coffinite and uraninite with minor amounts of paramontroseite and haggite. The ore minerals coat sand grains and fill interstices of complexly cross-stratified sandstone along solution fronts similar to "roll" type deposits of the other districts. Minerals of oxidized deposits are typically carnotite and tyuyamunite with different proportions of secondary vanadium accessory minerals. Ground water was the transporting medium and deposition of primary uranium and vanadium minerals occurred in reducing environments produced and controlled by physio-chemical characteristics of the sedimentary rocks.

Jan 1, 1968

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By Norman Brown, J. V. Rinnovatore

Substructures in explosively deformed and annealed ß brass have been examined by electron microscopy. In the explosively deformed condition, the structure contains a large density of straight screw type dislocations. Subsequent annealing up to 300oC produces low angle boundaries, which are characterized by superlattice dislocations, and expanded and contracted nodes. Evidence is given where two a(111) superlattice dislocations combine to form two a(001) superlattice dislocations. It is also shown that annealing at 400°C the networks disappear and that quenching from 400" C produces square and circular prismatic dislocation loops that lie on (100) and (111) planes, respectively. THE purpose of this work was to determine the effects of explosive deformation and subsequent annealing in a superlattice using electron microscopy. One of the first observations of explosively deformed structures was made by Hornbogen1 on a iron. Hornbogen found that screw dislocations were most prominent in the explosively deformed structure. He explained this result by suggesting that the edge components of dislocation loops move with the velocity of the shock front leaving a trail of extended screw components. Kressel and Brown2 observed explosively deformed Fe3A1, which is basically a body-centered type of superlattice in terms of dislocation geometry, and found that, as in the case of iron, screw dislocations were most prominent. It was also observed2 that, in cold-rolled and explosively deformed nickel, screw dislocations did not predominate, but rather a uniform network of dislocations was present in which the orientation of the dislocations was random. (Cell structures also have been observed by Nolder and Thomas3 for copper and by Johari and Thomas* for nickel). Kressel and Brown2 discussed the difference between dislocation morphology for bee and fee metals in terms of dislocation mobilities. They suggested that edge dislocations have a greater mobility than screw dislocations in bee metals but not in fee metals. Thus, the idea offered originally by Hornbogen1 is not valid since it should apply equally to fee and bee systems but does not. The results of recent work by Mikkola and cohens on explosively deformed Cu2Au are consistent with other observations for fee metals. They found that dislocations were randomly arranged but there was no significant cell formation. At high shock pressures, deformation twins are produced in fee metals.' High pressures in bee metal should induce the bee — fee transformation while the metal is under pressure. EXPERIMENTAL PROCEDURE The Cu-Zn alloy used in this work contained 51.4 wt pct Cu. Specimens of 0.5 in. diam and 0.012 in.

Jan 1, 1968

By J. D. Verhoeven

The effectiue distriblltion coefficient has been Measured in a series of vertical, normal freezing experirtzents with large current densities passing through the solid-liquid interface. The results indicate that the effect of the current on solute redistribution is due to electvotransport in the liquid. The high currents produced extensive mixing in the liquid which was considerably reduced by solidifying in small lubing. Analysis of the convection indicates that it probably vesulls from a horizontal temperature gradient produced by the Joule heating- of the electvic crirver~t. Due to the strong dependence of this convection upon the specimen radius, it is conclnded that only for specit~ens with radii of less than somewhere between 1 and 2 mm wilt electric field freezing be getlerally effec-tire at enhancing the purification of zone-melting experittierats in loe-melting alloys. Experiments on 0.8-mm lubes illustrate some interesting potential applications of this techniqne as a means of solute control on smcrll specimens. In a number of papers published within the last few years'-4 it has been found that passage of large dc currents through the solid-liquid interface of a freezing alloy produces a change in the solute redistribution accompanying the solidification. It had been predicted theoretically by Hucke et al.s and by Pfann and Wagner that such an effect would occur as the result of electrotransport within the liquid boundary layer at the solid-liquid interface. These authors independently derived the following relation between the effective distribution coefficient and the variables of the process: Where k0 is the equilibrium distribution coefficient, V is the mobility of the solute relative to the solvent, E is the electric field intensity, D is the solute diffusion coefficient, R is the rate of interface motion, and 6 is the boundary layer thickness. Both groups of authors show that this equation predicts the possibility of extending the purification ability of zone-melting experiments by the addition of an electric current. However, there are other effects in addition to electro-transport which could be produced by the high dc current and might, perhaps, invalidate the applicability of Eq. [I]. For example, high electric current might affect the interface reaction or perhaps the equilibrium distribution which was assumed to exist at the interface. It was the purpose of this work to determine the applicability of Eq. [I] by systematically investigating a simple system for which all of the necessary parameters were known. It was of particular interest for speculating on the potential usefulness of this technique to determine the maximum practical field intensities obtainable, and the effect of these high fields upon convective mixing in the liquid. The initial work in this study was published in a previous paper3 which will be referred to as I. In that work, a current density of 2000 amps per sq cm was used with specimen diameters of 5 mm. The results gave a qualitative confirmation of Eq. [I.], and also showed that a large amount of convective mixing was produced in the liquid by the current. The present study is an extension of that work to smaller specimen diameters and higher current densities. Two points were overlooked in I and will be emphasized here: a) the value of ko has not been well-established in the Sn-Bi system and b) the observed convection could be due to thermal convection produced from the Joule heating. EVALUATION OF k0 To evaluate Eq. [ I.] it is necessary to know the value of the equilibrium distribution coefficient, k,. Tn I the value of k, was taken as 0.3 from a published phase diagram.7 According to ansen' the best data on the phase boundaries of the Sn-Bi system are those of Davidson.5 The data of Davidson give a k, value ranging from 0.21 to 0.25 for the compositions studied in this work, or an average value of around 0.23. In a recent publication, Rigaud and Tougas'10 determined ko by means of a solidification technique. For an alloy of approximately the same composition as that used in this work they obtained a ko value of 0.39. Hence, there is considerable uncertainty in the value of ko and, consequently, a series of experiments were made to determine k, more accurately.

Jan 1, 1968

By M. J. Coolbaugh

Mining potash at depths of 3000 ft or more beneath thick water-bearing sediments in Saskatchewan presented a unique challenge to the North American mining industry. Potash is known to flow under pressure, but the knowledge of its flow characteristics at great depths was inadequate for safe design of mine workings and for assured protection from water above the salt formations. At the 3000-ft. depth of the Canadian mines, the potash is stressed beyond its elastic limit, and therefore mining design must deal primarily with its behavior as a plastic material. Recognizing that careful study would be required in order to assure safety and stability of mine workings in deep potash, IMC initiated an extensive rock mechanics investigation of structural properties of potash and salt under high-stress conditions. This presentation consists of a brief review of the development of some methods of testing potash in the laboratory and in the field; some of the rock mechanics concepts and principles derived; and their application to potash mine design. The mining of potash more than 3000 ft beneath the water-bearing sediments in Saskatchewan presented the unique challenge of designing stable mine workings and assuring protection from overhead water in a material that was believed to flow plastically, but whose behavior as a plastic material was not sufficiently known. Under the stress conditions ordinarily encountered in mining, most rocks behave as elastic materials; that is, they compress slightly under pressure, and rebound when the pressure is released. Salt and potash, however, are different. Even under the relatively low pressures encountered at shallow depths, these materials become slightly plastic and yield to stress by flowing.* The plastic properties become more pronounced at greater depth and pressure, and the question arises as to whether or not the plastic flow will be rapid enough and exert enough pressure to destroy underground structures or interrupt the mining process. It was found, however, that not only was there an insufficiency of information about the behavior of potash and salt, but conventional methods of testing these materials, such as determining the modulus of elasticity, Poisson's ratio, and uniaxial compressive strength, were inapplicable because of the high stress conditions prevailing at the 3000-ft depth. Potash under high pressure, for example, has practically no modulus of elasticity, its stress-strain relationship varies with time, and its compressive strength depends upon the degree of confinement. Elasticity and Stress/Strain Relationship: Fig. 1 shows a standard stress/strain chart for potash as made by the Department of Mines in Canada. Typically, when stress is applied to a hard-rock specimen, the specimen contracts, then expands to its original shape when the stress is withdrawn. This chart illustrates, however, that potash under stress yields to the stress by flowing, and does not expand when the stress is withdrawn. When the applied stress was held constant for 30 min, beginning at points A and C, the strain continued to increase and the potash flowed to points B and D, respectively. Points B, D, F, and H show that the potash did not return to its original shape when the stress was released. Thus it can be observed that potash has practically no elasticity and that the amount of strain depends upon the length of time that the stress is applied. Compressive Strength: The conventional method of determining the compressive strength of hard material is to find the maximum pressure that long slender specimens of the material can withstand without failing. As illustrated in Fig. 2,* line B, a standard 2-in. cube of potash subjected to a conventional type of uniaxial compressive test will exhibit a strength of about 5000 psi. However, the compressive strength exhibited can be made to change by changing the conditions under which the test is made. For example, if teflon plates lubricated with graphite are inserted between the press and the specimen, thus minimizing end constraint, the compressive strength is only about 2500 psi, shown in line A. If a specimen is cut in half, changing the width-to-height ratio to 2 : 1 instead of 1:1, and then tested without lubri-

Jan 1, 1968

By J. M. McKenzie

p-n junctions to detect and measure the energy of single quanta of electromagnetic radiation are described. Useful energy range is from 1 kev to several Meu. Achieved energy resolution varies from 30 pct at 6 keu to 0.12 pct at 2 Mev. Parameters affecting the perfornzance of the present detectors and desired of a new material are discussed. DURING the last 6 years semiconductor detectors have been used extensively to detect and to measure the energy of charged particles. These detectors are made from reverse-biased p-n junctions. Electron-hole pairs are created in the depletion region of the junction, Fig. 1. The carriers are separated by the electric field and give rise to a pulse of current in the external circuit. This current pulse is proportional to the number of carriers and hence to the energy deposited in the depletion region by the ionizing event. More recently the discovery of the lithium drift process, first in silicon' and then in germanium,2 has extended the use of semiconductor detectors to the detection and the energy measurement of single quanta of electromagnetic radiation. These detectors now have a useful measurement range extending from the soft X-ray region, about 6 kev, to the hard y ray region of several Mev. Surface-contoured avalanche diodes can be used to extend this range down to 1 kev. There is however a desire for other materials suited to higher operating temperatures, and particularly for those materials with high y ray stopping power. The most important advantage of the semiconductor detector over gaseous and scintillation detectors is the average energy, E, required to form an electron-hole pair. Fig. 2 shows the quantum efficiency for germanium as a function of photon energy.3 At the band-gap energy, 0.7 ev, an electron-hole pair is generated by the absorption of the photon and the quantum efficiency is unity. The quantum efficiency remains constant at unity between 0.7 and 3 ev. It then increases as additional electron-hole pairs are formed by secondary ionization of the initial photoelectron. The rate of increase is about 1 electron-hole pair per 3 ev (actually 2.9 ev for germanium and 3.6 ev for silicon). This figure is constant irrespective of the particle type (electron, proton, a particle, heavy ion) and energy. In an ionizing event an incident particle of energy E will create N = E/e ion pairs. The statistical fluctuation in this number is proportional to &. The fractional energy resolution is therefore proportional

Jan 1, 1968

By Thomas C. Atchison

An understanding of the physical processes involved in breaking rock with explosives will lead to better blasting techniques. In this chapter known rock breakage principles will be outlined, some conjectural ideas will be discussed, and areas needing further study will be pointed out. The principles outlined will serve as a basis for the design of blasting rounds described in the following chapter. 7.2-1. Factors Important to Rock Fragmentation. The efficacy of explosives as tools for rock fragmentation lies in their ability to deliver almost instantaneously large amounts of energy to a limited portion of the rock. When an explosive charge is detonated in a drill hole, its energy is released in a very small fraction of a second in the form of gas at extremely high pressure and temperature. The mechanics of the transfer of this energy to the rock and the resulting breakage are complex and not completely understood. Factors that have been identified as important to the fragmentation process may be grouped in three categories: explosive parameters, charge loading parameters, and rock parameters. EXPLOSIVE PARAMETERS. Explosive parameters known to influence breakage are density, detonation velocity, detonation impedance, detonation pressure, gas volume, and available energy. Detonation pressure is probably the best indicator of an explosive's ability to break solid hard rock. Detonation pressure is roughly proportional to the product of density and the square of the detonation velocity. The relative ability of different explosives to transmit their pressure to stress in a given rock is function of their detonation impedances. Detonation impedance is the product of density and detonation velocity. The volume of gas released in the explosive detonation undoubtedly is of importance, at least in the later stages of breakage, and is probably

Jan 1, 1968

By J. Clair, H. Mirabel

The determination of the temperature and electrical potential distributicms in the cathodes of aluminum electrolytic cells is difficult. The reascms come from the various nature and the intricate three-dimensional geometry of the materials; besides thermal and electrical phenomena react upon each other. A method of calculation using a computer program applied to a mathematical model, figuring the cathode, is developed. Both of the thermal and electrical phenomena are simultaneously considered. Temperature and electrical potential distributions are finally obtained by successive iterations. Results are compared with measurements on industrial cells. Theoretical and practical applications of these studies are given. Up to the present time the study of the distribution of the temperatures and electric potentials in the electrodes, anode and cathode, of the electrolytic cells used for the production of aluminum was limited to one of the two aspects of the phenomena because of lack of a simultaneous method of calculation. For example, the anode or cathode drop was studied assuming that the temperatures in the iron and carbon are known, a method that obviously is very approximate since iron resistivity, in particular, greatly varies with temperature, which in turn depends on current density. Consequently we tried to find a method of calculation simultaneously taking into account both thermal and electrical phenomena. We proceeded to the study of the cathodes as an initial approach to the problem. Although the cathode and surrounding materials may have varied forms and particularly very heterogeneous characteristics, their structures are simpler than that of the Sijderberg anode and boundary conditions are more easily represented than in the case of anodes even though they are prebaked. The study was in two parts: a) development of a model schematizing the true geometry of a cathode and defining the thermal and electrical boundary conditions, and b) working out a method of calculation of the temperatures and potentials by means of an electronic computer. To facilitate solution of the problem, a model was used initially much simplified in comparison with an actual cathode. This model permitted development of the method of calculation. In a second phase, this model was adjusted to the study of actual cathodes and applied to different types of cells: low- or high-intensity cells, cells set up at ground level or above ground level, cells with cathodes more or less heat-insulated. Simultaneously measurements were made with cells equipped with cathodes of the types studied to compare the values resulting from calculation. The initial model was also used for general studies, in particular for studying the effects of current density in the carbon and iron. The results were confirmed or made precise by the model of the true cathodes. This report successively describes: a) the manner in which the model representing a cathode was worked out, with the simplifications and/or the hypotheses used, b) the method of solution of the problem by means of the electronic computer, and c) an example, stating the extent to which the results obtained may be realistic. Further the possibilities offered by such a study are examined. 1) CATHODE REPRESENTATION The purpose of this phase is to represent the cathode in the form of a so-called "mathematical model", that is with a simplified geometrical configuration, in order to meet the subsequent calculation requirements, while keeping to the true facts as closely as possible. This model further includes the thermal and electric conductivities with regard to temperature for the varied materials composing the cathode, as well as the thermal and electrical conditions at the model boundaries. 1.1) Guiding Principles. For calculating the temperatures and potentials the model is divided by trior-thogonal planes into a network of small elementary parallelepipeds. At the summit of these parallelepipeds' so-called mesh points, the temperatures and potentials are computed. The number of mesh points is of course limited by the capabilities of the computer, since 1) the number of equations to be solved depends on the number of mesh points selected, and 2) the amount of time spent by the computer considerably increases with increasing this number. These conditions call for the following requirements as concerns the model: a) Dimensional requirements: the calculation will be all the more accurate as the network is more closely meshed. Since the number of mesh points is limited in practice, it is necessary to restrict the dimensions of the model. b) Geometrical requirements: so as to make things easier in working out the network, the model must be given a simple geometry. In particular, it will be convenient to have the cathode so constituted that the surfaces limiting the cathode and the surfaces within the cathodes separating the different materials consist of triorthogonal planes. 1.2) Schematization of the Cathodes. After the tech-

Jan 1, 1968