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By K. F. Veit, R. L. Marovelli, T. S. Chen

There is an error at the bottom of the right-hand column of p. 11, and the top left-hand column of p. 12. The first paragraph of the section EXPERIMENTAL RESULTS should read: "Thermal shock tests were conducted on circular discs of basalt, quartzite, and taconite. Average grain sizes ranged between 0.10 and 0.25 mm. Individual discs were tested only once, either in a cooling or heating shock. Several discs of the same rock type were shocked at a temperature, and the temperature level then was increased for another test by 10° to 20°F until complete fracture occurred when a specimen was quenched. The minimum temperature difference required to initiate cracking, TmiN was observed and used, together with other property values, to compute the dimensionless stress o*max . The observed ?Tmin for cooling shock in different media is tabulated in Table I. The property values E, St, a, and K are shown in Figs. 6, 8, 10, and 11, respectively. Discs of various rocks shocked in different isothermal baths gave o*max values for a wide range of Biot numbers. These o*max values were then compared with the theoretically predicted values."

Jan 1, 1968

By Y. A. Chang

Heat content values of tantalum monocarbide and tungsten monocarbide have been determined from 325" to 985°K by means of a drop-type diphenyl ether calorinzeter. Based on the values obtained in the present study and those available in the literature, best values lected and computed from 298. 15°K to temperatures close to their respectiue melting points. At temperatures higher than 1700°Kfor TaC and 27000 K for WC, values of Cp and related thermodynamic quantities were extrapolated based on the two Debye parameters: one corresponds to the metal sublattice and the other to the carbon sublattice. The contrzbutzon In the total specific heat due to lattice dilation was evaluated using the Nernst-Lindemann relalionship. The calculated values of Cp were in good agreement with the In view of their refractoriness, tantalum monocar-bide (TaC) and tungsten monocarbide (WC) are of con- experimentally determined ualues. Furthermore, the calculated values of the absolute entropies at 298.15"K were 5.03 and 4.15 in comparison to the experimental values of 5.05 and 4.15, all expressed in the unit of cal per degg-atom. Using the same Debye parameters, values of the linear coefficients of ther mal expansion for TaC and WC were calculated from absolute zero to their respective melting points using the Grüneisen equation. The calculated values are in excellent agreement with the experimental values available in the literature. Finally, the values of the bulk modulus of TaC from room tenzperature to temperature near its melting Point were also calculated using the equation recently derived by Anderson. No cot~ipari-son between the calculated and experimental values can be made due to lack of experimental data. siderable practical interest. In order to completely define these materials, it is necessary to know their thermal properties as a function of temperature. Tantalum rnonocarbide having a NaCl structure (B-1 type) melts congruently at 4250PK,1 while tungsten monoearbide with a simple hexagonal structure (Bh type) melts per itectically at 3049°K into melt and graphite.2 In the present study, the heat content values (from which

Jan 1, 1968

By Louis G. Bailey

This paper .reviews some of the key developments which have been made in the synthesis of the III-V compound semiconductors and the associated progress in obtaining high-quality material for device development. The history of the investigation of the semi-conducting properties of these materials has indicated the need for synthesis techniques capable of producing rnaterial of high chemical purity and physical perfection. The progress in the area is described, and the present status of quality of several compounds is discussed. In addition, recent studies of localized epitaxial deposition of GaAs into semi-insulating GaAs substvates for the development of arrays of devices ave reviewed. In conclusion, some important areas for future research and developrnent are discussed. INTEREST in III-V compounds as semiconductors dates back to the period 1950 to 1952, when Goryunova, Ioffe, and, in particular, Welker determined that 111-V compounds were structural analogs of the group IV elements carbon, silicon, germanium, and tin and that they were also semiconductors.'-3 Since that time interest in the properties of these materials has ex- panded rapidly. During 1953 and 1954, the first reports of rectification, photoconductivity, and optical absorption in these materials came from several investigators. In 1955, recombination radiation from samples of GaAs, InP, and GaSb was reported by ~raunstein .' This radiation was produced by injected minority carriers from point and large-area contacts. From 1955 to 1960, efforts increased on preparing large, pure specimens of these materials for the study of basic physical phenomena and device exploration. By 1960, materials preparation and the understanding of the physics of some of the materials had advanced to where some very interesting and potentially useful phenomena came under study. The first observation of electric-field-induced changes in the optical absorption edge (Franz -Keldysh effect) of 111-V compounds was reported for GaAs by Moss in 1961.' In 1962 the study of recombination radiation advanced rapidly. Keyes and Quist6 and Pankove and Berkey-heiser7 reported high radiative efficientices obtained from recombination, and then the first injection electroluminescent lasers in GaAs were announced by Hall ef al.,' by Nathan et al.,O and by Quist ef al.,'O and in Ga(As, P) alloys by Holonyak and Bevacqua." Hil-sum has reviewed the early work leading to the first observations of laser action in GaAS." Recombination processes in GaAs, Gap, and the other 111-V com-

Jan 1, 1968

By S. F. Bartram, G. A. Chase

COMPUTED X-ray diffraction powder patterns of YNi3, YNi5, and CbBe3 are available on request from either author.

Jan 1, 1968

By Paul Cherin

ThE angle of intersection, 0, between h2k2l2 planes and the (loo), (110), (101), and (111) planes was calculated on an IBM 7040 using the well-known relationship

Jan 1, 1968

By Ronald C. Koo

SMALL additions of potassium, aluminum, and silicon as oxides (referred to as dope) to tungsten have been known for several decades to have a very large effect in raising the recrystallization temperature and altering the recrystallized grain morphology of heavily drawn wire. Previous investigations of this doping effect1 6 have led to various speculations but all failed to deduce unequivocally the physical state or the mechanistic influence of the dopant. Recently, walter7 has observed, by transmission electron microscopy, strings of "fine particles" in heavily rolled and annealed doped tungsten sheet and concluded that they were particles of mullite (Al6Si2013). His conclusion was inferred from the electron diffraction patterns of large particles ex-trated by carbon replication of fractured surfaces of slabs rolled from sintered ingots. That the strings of "fine particles" in heavily rolled and annealed sheet were also mullite was an assumption for which no evidence was presented. A similar investigation has been carried out in this laboratory over the past 2 years on a variety of tungsten wire: doped tungsten, and undoped tungsten, as well as 218 doped tungsten purchased from the Lamp Metals and Components Department of the G.E. Lamp Division. Although the electron microscope observations are similar to those reported by Walter, the writer has reached a different conclusion concerning the physical state of the dopant in annealed tungsten. The purpose of this communication is to present evidence that the strings of "fine particles" observed in transmission specimens are not mullite, but are voids. In the present investigation, tungsten wire, 0.88 mm in diam, was rolled into ribbon 0.2 mm by 125 µ thick. The ribbons were annealed in vacuo at a pressure of -1 x 10-5 Torr and then thinned electrolytically in a 2 pct KOH solution. Fig. 1 shows a typical transmissicjn electron micrograph of a sample annealed at 1700°C for 30 min which reveals rows of closely spaced voids having a light contrast (referred to as "fine particles" by Walter) aligned parallel to the working direction. Stereo micrographs (by D. Moon, Westinghouse Research and Development Center) have shown that these voids do not exist on the surfaces of the specimens as a result of thinning but are within the thin-foil specimens. The following experiments have been performed to verify that these are indeed voids. I) Effect of Annealing. Voids are absent in unannealed specimens and appear only after annealing. This behavior cannot be explained if they were solid particles such as mullite. Precipitation (in an unquenched specimen) upon annealing requires solute elements having decreasing solubilities with increasing temperature. Although the solubility of aluminum in tungsten does decrease with increasing temperature, precipitation requires a concentration in excess of 1.4 wt pct,8 which is at least two orders of magnitude higher than the aluminum content in doped tungsten. It is also unreasonable to assume that particles aligned in rows initially present in unannealed specimens were too

Jan 1, 1968

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

The temperature, orientation, and strain-rate dependence of tensile flow in single-crystal NiA1 of equiatomic composition have been investigated up to 800°C. Compression tests at room temperature have also been carried out. Optical and replica electron microscopy and X-ray diffraction methods were used to investigate the slip mechanisms. NiAl exhibits {110)(001) slip and cube slip {l00)(010) was also observed. This results in very high strength of single crystals in cube orientation. The implications of this slip mode, with the resultant small number of possible slip systems and three mutually perpendicular slip vectors, are discussed. ThE CsCl structure compounds represent a class related to the bcc elements, but their behavior is affected by three additional variables: composition (within the stability range of the compound), extent of long-range order perfection, and bonding energy. Very little data are available on the effects of these variables on mechanical properties. Rachinger and ~ottrell' suggested slip to occur along (111) in compounds of low ordering energy; in compounds of higher bond strength (>0.06 ev), they observed (110) (001) slip. As pointed out by copley,' only three in- dependent slip systems are available in the latter case; hence general deformation is impossible. Brown3 carried out a theoretical calculation of the yield-point variation with the degree of long-range order in the CsCl structure, based on the assumption of superdislocations. More general approaches, based on considerations of superlattice dislocations and antiphase domain boundaries in ordered structures, were carried out by Flinn~ and by Vidoz and Brown.' These, however, give no information on changes in the slip structure—if any—between the ordered and the disordered compounds. This aspect was investigated experimentally and theoretically by Stoloff and Davies' and by Marcinkowski and chessin7 in FeCo. The latter workers proposed the deformation behavior of the ordered FeCo to be essentially the same as that in many other bcc metals. Investigations of polycrystalline A~M~'-'O indicate considerable variation in mechanical properties with composition and test temperature. The existence of {123)(111) slip was reported in AgMg.'9'9'0 (The formation energy of this compound, presumed to be ordered at all temperatures below melting, is 4.38 cal per g-atom," i.e., 0.024 ev per bond.) The yield strength has been reported as relatively independent of temperature below 0.45 T, (where T, is the absolute melting temperature). Tensile deformation of single-crystal AgMg was also investigated by Kurf-man," who observed marked tendency to single glide on{112}(111) and {110)(111). From observations of slip lines in deformed poly-crystalline NiA1, Westbrook et a1.I3 suggested the

Jan 1, 1968

Jan 1, 1968

By N. A. D. Parlee, M. M. A. El-Naggar, G. 8. Horsley

The apparatus was of a modified Sieverts type1&apos;2 with a reaction tube designed to function also as the cell component of an oxygen pressure gage. The reaction tube assembly is shown in Fig. 1 and described in Table I. The main body is a 1-in.-OD 15 mol pct calcia-stabilized zirconia tube. The ground-glass joint, g, the male part of which carried a prism for optical pyrometer use, was connected to the remainder of the Sieverts apparatus. The calibration of the cell (at its 1000°K operating temperature) for internal oxygen pressures (PO2in) in the range 0.2 to 10 9 atm was made against internal air pressures measured by mercury manometer and McLeod gage. At very low po2in values down to l<Tn atm the performance was checked by comparing pQ calculated from electromotive force measurement when the apparatus was filled with a) pure CO gas and b) a CO-CO2 mixture of the ratio CO-CO2 = 1:0.398, with Po, values calculated from the equilibrium constants of the following reactions at 1000°K:

Jan 1, 1968

By D. G. Westlake, U. F. Kocks

WHILE single crystals of most materials with cph lattice structure show essentially unlimited ductility, polycrystalline specimens of the same materials exhibit the entire range of ductilities. A difference between the ductility of single crystals and polycrystals may be associated with the special stress concentrations to be expected, for example, at the intersections of slip bands or twin lamellae with grain boundaries. Whether such stress concentrations prove catastrophic depends on the cleavage strength of the material, the size of the stress concentrations, and the speed with which they are formed. Thus, the ductility may vary in degree from material to material. Another possible reason for differences in ductility between single crystals and polycrystals is that a sufficient number of independent deformation modes must be available to insure compatibility between the macroscopic strains in neighboring grains.&apos;&apos;2 This criterion is often taken to be a necessary condition for any polycrystal ductility whatsoever, not as one that determines different degrees of ductility; thus, a material with an insufficient number of independent deformation modes would have to be brittle as a polycrystal. The "sufficient number" is five if every grain is to accommodate arbitrary shape changes ("von Mises criterion "). We should like to argue that fewer than five independent modes may be sufficient to satisfy compatibility conditions; and that the internal stresses set up when the plastic strains are not compatible reach the theoretical fracture stress only after a significant amount of macroscopic strain has taken place which may vary in magnitude from case to case, allowing an influence on the degree of ductility. Experimental evidence for these statements is taken from the following review of the number of independent deformation modes observed in the various cph

Jan 1, 1968

By John K. Hammes, Stanley D. Michaelson

The material presented in this chapter is supplemental information on those significant aspects of open-pit copper mining that are to an extent unique and therefore not detailed in previous sections covering the fundamentals of open-pit mine planning, operations and maintenance. In addition, tabulated cost and operating data are presented for a variety of open-pit copper mines. 13.3-1 History. The history of the civilized use of copper began at the end of the Stone Age when man discovered that the red metal, in the form of native copper, could be readily worked into a variety of weapons and tools which simplified the primitive requirements for survival. Almost concurrently, the high value of these early copper products became so widely known that they soon assumed major importance as trading commodities. Copper and copper-alloyed artifacts, even though produced in very limited quantities by ancient miners and metalworkers in a few parts of the Near East and the Western Hemisphere, were so valuable that early warriors and traders carried them into nearly all the world&apos;s known areas of importance. As far as copper is concerned, the Bronze Age, at sometime around 8000 BC to 6000 BC, marked the vague, little-known beginning of metallurgy. Man learned to alloy the valuable red metal to make it harder and tougher; its use multiplied as did the variety of weapons and tools made with the gradually increasing metallurgical and fabricating skills. By 3000 BC bronze alloy products became relatively widespread ; copper mining activities assumed tremendous importance and the mines on the Isle of Cyprus developed into prized possessions of each Mediterranean empire from the times of Egyptian supremacy to well beyond the decline of the Roman Empire.

Jan 1, 1968

By R. H. Richman, F. Borik

A 0.3 pct C-12 pct Cr-6 pct Ni steel was rolled to 93 pct reduclion in area as austenite at 510°C, and then partially transformed as desired to ~rlartensite by qnenching to - 196°C. Pole figures for the austenitic matrix and for the martensitic product were separately determined by an X-ray transmission method. The deforitration texture of&apos; the warm-worked austenite is characlerized by (110)(225) components, and is thus closely similar to those produced in a brasses. The pole jigure of the martensite in partially transformed material agrees well with that which can be constructed by transfortnation of the {110)(225) orientations according to either the Kuvdjuniov- Sacks or the Nishi-yatuu relatiotship. Howeuer, an important result of this construction is that me-third of the predicted orientations are missing. A graphical analysis can then be used to show that in deformed austenite certain crystallographic variants of martensite (related to the most probable austenite slip systems) are suppressed, resulting in this preferred transformation. The evidence for preferred transformation is corroborated by the measured elastic anisotropy of warm-rolled and fully transformed H-11 steel. EXTENSIVE plastic deformation of a polycrystal-line aggregate in a manner that causes flow predominantly in one direction results in a preferred orientation of the constituent crystallites. The particular orientations that are produced depend upon the crystal structure and composition of the material, as well as upon the temperature, mode, and degree of deformation; in any case, the preferred crystallo-graphic orientations, or textures, are reflected in directionality of mechanical properties. Although such anisotropy may be exploited in certain specialized applications, it is more commonly diminished or eliminated by heat treatment lest it interfere undesirably in subsequent forming operations or in structural design. In the recently developed thermomechanical treatments that significantly enhance the strength of some steels,1,2 considerable deformation of the metastable austenite prior to the martensite transformation is essential to the strengthening process. If the austenite is textured by the deformation, and if the transformation to martensite proceeds according to one of the relationships established for transformation in annealed austenite, then it must be expected that the martensite will also possess a preferred orientation even though the multiplicity of martensite orientations possible in a given austen- ite crystal will tend to restore some degree of randomness. The existence of a residual anisotropy, both mechanical 3-6 and crystallographic,&apos; has been substantiated. In the latter crystallographic investigation, preferred orientations were determined for the martensitic structure of an SAE 4340 steel rolled 72 pct as austenite at 833°C and then quenched. However, the choice of a composition that transformed almost completely to martensite during the quench to room temperature did not permit direct measurement of the prior austenitic texture. In fact, when the "ideal orientations&apos;&apos; associated with well-known fcc rolling textures were converted, alone or in combination, to martensite according to the Kur-djumov-Sachs (K-s)&apos; or Nishiyama8 relations, the agreement obtained with the observed martensite texture was only fair at best. Recently a pertinent aspect of the austenite to martensite transformation was reported by Bokros and parker,10 who found that certain habit-plane variants of martensite were suppressed by tensile deformation of Fe-31.7 Ni single crystals prior to the necessary subzero cooling. It might be anticipated that the consequences of such preferred transformation are sustained during the formation of martensite in warm-worked austenite that has a well-developed deformation texture. The present investigation was undertaken first to establish more firmly the relation between preferred orientations in plastically deformed austenite and in the resulting martensite, and second to examine the textures for evidence of deformation-induced preferred transformation. EXPERIMENTAL PROCEDURES An alloy containing 0.3 pct C, 12 pct Cr, 6 pct Ni, and the balance iron, was selected because the mar-tensite-start temperature (M,) of about -100°C allowed convenient experimental manipulation of either austenite or martensite at room temperature. Furthermore, this composition can be readily deformed as metastable austenite at moderately elevated temperatures without intervention of appreciable isothermal or athermal decomposition products. The alloy was austenitized at 1150°C, aircooled to 510°C, rolled unidirectionally at this temperature to 93 pct reduction of cross-sectional area, and finally oil-quenched to room temperature. Partial transformation to martensite was accomplished by quenching to -196°C as needed. The rolled stock was reduced in thickness from 0.067 to 0.010 in. by etching in a solution of 5 pct HC1, 45 pct HNO3, and 50 pct water, and further thinned by careful mechanical polishing to maintain the two sides of the sheet parallel within 0.0003 in. After mechanical polishing to 0.005 in., electropolishing in 1:9 perchloric-acetic acid solution produced a final thickness of 0.002 in. The preferred orientations were determined from

Jan 1, 1968

By G. R. St. Pierre, L. M. Adelsberg, R. Speiser

The rate of scale fot&apos;~I~ti0n on tantalum held in H20-Hz-Ar gns mixtures at temperatures between 840" and 1250°C is related to gas composition and ternpevature. It is found that water vapor partial pressure determines the oxidation rate at a given temperature and that the oxygen potential as fixed by the water vapor to hydrogen ratio Ins no significant effect on the oxidation rate. The Ta205 scale formed during oxidation is composed of an inner lattice-dijf~ision barrier and an outer layer of- cracked/porous oxide 1 HE oxidation of tantalum at temperatures less than 800°C is characterized by solution of oxygen into the metal,&apos;-&apos; the formation and growth of suboxides into the metal,&apos;)2~10-15 and the delayed nucleation of the highest oxide, Above 800°C, Ta205 is found to nucleate rapidly10, 11, 15, 16 except at low oxygen pressures:15 however, there is uncertainty regarding which does not retard the oxidation process. For each gas con~position and temperature investigated, the oxidatioz rate becomes constant after a short adjustment period. It is shozm that a constant oxidation rate nzay pre~?ail even though the tlzickness of the inner lattice-dijjitsion layer of Ta205 is clanging. TFze initial czcrz!ature of the typical &apos;Paralinear" oxidation curve may result froprz causes other than an increasing thickness of tlze inner protective layer. the detailed mechanisms of the high-temperature oxidation. Peterson, Fassell, and wadsworth17 observed linear oxidation behavior for tantalum in oxygen at temperatures between 600" and 1000°C. They reported that equilibrium adsorption of 0, occurs on a surface prior to the rate-deter mining step of the reaction. Cowgill and stringer1&apos; confirmed the observations of Peterson and his coworkers. They stated that the rate-determining step of the reaction could be either the incorporation of adsorbed oxygen into the anion lattice or the dissociation of 0, at the gas-oxide interface. The relative rates of the two surface reactions were proposed to be dependent upon the reaction temperature and the oxygen pressure. stringerlo subsequently reported that the reaction surface is located somewhere

Jan 1, 1968

By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper&apos; covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.&apos; It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.&apos;" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By D. Dever, E. S. Fisher

Measurements of the temperature dependence of the elastic moduli in single crystals of hep ruthenium, rhenium, cobalt, dysprosium, and erbium were carried out for various temperature ranges so as to investigate the correlation, suggested by prior work, between the shear anisotropy ratio, A = C44/C66, and the occurrence of the hcp — bee phase transformation. These measurements confirm the suggestion that A has a positive temperature dependence in that group of hcp metals that undergo thermally induced transfornzations to the bee structure and a negative or zero temperature dependence in the other hcp metals. It appears, from indirect evidence, that the hcp -fee transformation in cobalt is preceded by a highly negative temperature dependence of A. These results indicate that elastic anisotropy is an important factor in determining the temperatures at which martensitic phase transformations occur. Two possible roles for elastic anisotropy are proposed: 1) the shear-modulus ratio within the habit planes must be nearly similar for the two phases and 2) a large anisotropy decreases the stress necessary for the movement of the transfornzation dislocations. FUCHS&apos; calculations of the elastic moduli in the alkali metals have shown that the high shear-anisotropy ratios, c/c&apos;, in certain bee metals and alloys are the result of large negative contributions to c&apos; = (c11 - c12)/2 arising from the nearest-neighbor repulsive forces.&apos; On this basis, and following Zener,2 the association between high c/c&apos; ratios and the martensitic phase transformations that occur upon cooling certain bee metals is explained as a unique characteristic of the bee structure. Recent measurements of the elastic moduli in hcp titanium and zirconium show, however, that a high elastic anisotropy also exists in these hcp structures at the temperatures at which they transform to bee upon heating3. If there exists a direct and consistent correlation between the elastic anisotropy in close-packed structures and the occurrence of transformations to the bee phases then there is evidently a need to re-examine the conclusions of Zener theory. Elastic anisotropy may also be the result of the effects of temperature on the stability of the low-temperature close-packed structures or it may play an important role in the mech- anism of the martensitic transformations. The present measurements were aimed at establishing the phenomenological correlation between elastic shear anisotropy in hcp structures and the thermally induced hcp —bee transformations that occur in the majority of the twenty-three hcp metals, as shown in Table I. Prior to the present work the temperature dependence of the anisotropy ratio, A = c44/c66, was known at various temperatures for nine of the metals listed. The data showed a negative temperature dependence of A for cadmium, zinc, magnesium, and cobalt, which do not transform to bee, and a positive temperature dependence of A for thallium, zirconium, titanium, hafnium, and yttrium. The correlation was, however, ambiguous in that these two groups of metals are also separated with respect to the c/a ratios as noted in Table I. There remained the possibility that the temperature dependence of A is a function of c/a and not consistently associated with the transformation. The measurements of the elastic moduli in rhenium and ruthenium, in which hcp —bee transformations do not occur, were needed to help decide this question. The studies of dysprosium and erbium were undertaken to determine whether the correlation holds for the heavy rare earth metals.

Jan 1, 1968

By V. Lessels, D. J. Buckwalter, D. H. Rose

A cyanide leaching process developed at Michigan Technological University was tested in a 12 to 24 tpd pilot plant. Flowsheet layout and equipment are described. Cyclic operation of leaching, copper precipitation by acidification, and regeneration of the cyanide leaching solution are discussed. Copper extraction and reagent consumption were as predicted by laboratory tests, and the process was proven to be technically feasible. The White Pine Copper Co., a wholly-owned subsidiary of the Copper Range Co., produces copper in the Upper Peninsula of Michigan. Production in 1965 amounted to 138 million pounds of metal. An expansion program now under way will increase this by approximately one half. The highly mechanized room and pillar mine produces 18,000 tons of ore per day, which is treated in a flotation plant. The concentrate is smelted in a reverberatory furnace, the matte is blown in converters to blister copper, and the blister copper is further refined to a uniformly high-quality Lake copper, which is 100% conductive and has a silver content of 25 to 40 oz per ton. The run of the mine ore averages 22.5 lbs of copper per ton with the ore mineral occurring in the form of chalcocite. The nature of the mineralization is such that the sand tailings average a little over 4 lbs of copper per ton. Intensive research has improved copper recovery in the flotation operation to some extent, but at the scale of present operation about 12,000 tons of sands containing over 48,000 lbs of copper go to the tailings pond daily. When the plant expansion is completed, the loss of copper will be somewhat greater. In 1959, the White Pine Copper CO, initiated a study of the recovery of copper in the sand tailings. Inasmuch as the flotation operation was considered to be optimized, a logical approach seemed to be leaching. For various reasons ammonia, ferric chloride, acid, and biological leaching were ruled out as impracticable. This led to a consideration of cyanide leach-

Jan 1, 1968

By Daniel R. Shawe

Large tabular beryllium deposits in waterlaid rhyolitic tuff at Spor Mountain, Utah, contain the world's largest known resources of beryllium (as bertrandite). The district also has produced fluorspar and uranium. The largest beryllium deposit is about 2.5 miles long, and known deposits contain many million tons of material with at least 0.5 per cent BeO. The beryllium-bearing tuff (Pliocene?) underlies topaz-bearing rhyolite ( Pliocene?) that contains unusually high amounts of beryllium, fluorine, and uranium, and overlies other volcanic rocks (Pliocene? or Micocene?) and marine carbonate and elastic rocks ( Paleozoic). The deposits occur in hydrothermally altered tuff only where it contains abundant carbonate pebbles eroded from the Paleozoic rocks and where the tuff was deposited as thick layers in now-buried paleovalleys. Basin and Range faults, thrust fa ults, and possibly strike-slip faults formed in this part of the Basin and Range province during the late Tertiary, and volcanic rocks were extruded. Beryllium mineralization probably occurred during this episode. Undoubtedly the beryllium deposits are related genetically to the topaz-bearing rhyolite, but the details of their genesis are not certain and probably are complex. Beryllium deposits are close to major faults, and locally the beryllium is concentrated at faults, indicating fault control of mineralization. Some elements in the deposits, such as lithium, however, are evenly distributed in certain Luff beds and perhaps were introduced prior to faulting. Still other elements, such as manganese and lead, were concentrated in the beryllium deposits and subsequently were leached along late fractures, indicating a period of metal redistribution following mineralization.

Jan 1, 1968

By Sunder S. Saluja

Man had to learn to break rocks as early as the Stone Age, when they formed his main source of raw material. He started with chipping and over the years has reached a stage where he can employ atomic blasts and break, with one blast, millions of tons of rock. In between these two extremes there have been several stages of development including firesetting, use of the expansion of water on freezing in chipped cracks in cold climates, the use of low or deflagrating explosive black powder in about the 17th century, the use of high explosives with the discovery of nitroglycerine in 1846 by Sobrero, followed by the monumental discoveries of the great Swedish scientist Alfred Nobel in the latter half of the nineteenth century. The attempts to develop a stronger and still stronger explosive force were accompanied by investigations to understand the mechanism of failure of rock so that the force could be used to the best advantage; the latter, of course, have lagged far behind the former. This is mainly due to the fact that the chemical reactions involving high explosives as well as the processes resulting in the breakage of rock take place at too great a rate to be studied with the equipment that has been only recently available. Moreover, the development of stronger explosive forces was prompted by military necessities in the past and competition, at present, among highly developed nations. With the development, however, of the new techniques such as micro- second photography, microsecond flash radiography, extremely high-speed movies, strain gage assemblies, electronic chronographs and other improved electronic techniques, the investigator has in the last decade or

Jan 1, 1968

By Glenn C. Waterman, Scott Hazen

3.1-1. Purpose. Development drilling is directed towards determining the grade, volume, and three-dimensional outline of a mineralized zone previously located by exploration. It is distinguished from exploration or reconnaissance drilling, which has as an objective the discovery of new mineralized areas. A development drilling and bulk sampling program should furnish the following information: 1. Geology of the mineralized zone. 2. Quantitative data on grade and tons of material within pertinent cutoff limits. 3. Physical size and shape of the deposit. Areas underlain by waste as well as ore. 4. Mineralogica1 and metallurgical characteristics of the ore. 5. I1hysical characteristics of the ore. 6. Hulk samples for metallurgical testing and grade check. 7. Data on other factors that could affect mining operations, such as ground water, ground conditions, etc. 3.1-2. Procedures. There are numerous methods and techniques that are used to acquire pertinent data on a potential ore deposit. The total cost and accuracy of a development program depends on significant evaluation of the geology, proper selection of a drilling method, thorough analysis of sample data, and accurate evaluation of all the information. Knowledge of the geology of the mineral deposit is important in planning the development testing program and in evaluating the data obtained from such a program. Exploration work usually provides some significant information on the general size, shape, thickness, grade, and geology of the deposit. In some cases no further data are needed; in many cases geological complexities suggested by the preliminary work require further geological study. Of considerable importance may be the following:

Jan 1, 1968