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By R. W. Boyle

"The concept of using chemical methods in prospecting dates back at least to the middle of the 16th century. Modern methods of geochemical prospecting, however, based on secondary haloes and utilizing trace-element techniques, were first practised in the U.S.S.R. and the Scandinavian countries in the 1930's. After 1945, methods based on soils, stream sediments and vegetation were rapidly developed in the U.S.A., the United Kingdom, Canada, France and other countries.The modern methods of geochemical prospecting owe their rapid development in the 20th century to the following:1.-Recognition of the primary and secondary dispersion haloes and trains that are associated with all mineral deposits. 2.-Development of accurate and rapid analytical methods utilizing the spectrograph and the various specific sensitive colorimetrie reagents, especially dithizone. 3.-Development of polyethylene laboratory ware of all types and the development of resins. This permitted greater freedom of field analyses and reduced the incidence of contamination.4.-Development of gas chromatography. This permitted the rapid and accurate determination of hydrocarbons in petroleum prospecting.Future research in geochemical prospecting should be focused on the following tasks: 1.-Definition of geochemical provinces and their relation to mineral deposits. 2.-Development of methods for discovering large low-grade deposits. 3.-Development of methods for discovering deeply buried deposits. 4.-Further development of methods to outline primary haloes. 5.-Eiucidation and formulation of techniques to relate the size and intensity of anomalies to the grade of the deposits. 6.-Development and refinement of biogeochemical methods, especially those based on indicator plants, chlorotic or toxic effects, and microbiological techniques. 7.-Definition of the types of primary and secondary haloes associated with accumulations of oil and gas."

Jan 1, 1967

By J. W. Spretnak, J. N. Cordea

The gain boundary relaxation in high-purity aluminum, nickel, copper, and silver was studied by means of a low-frequency torsion pendulum. Both internal friction and creep at constant stress tests were conducted. A lognormal distribution in relaxation times was found to account for the relatively wide experimental internal friction peaks and the gradual relaxation behavior during the creep tests. This distribution was separated further into a lognormal distribution of relaxation time constants and a normal distribution in activation energies. A spread of up to ±6 kcal per mole in the activation energies accounted for the major part of the distribution. A "double-peak" internal friction phenomenon was observed in silver. The activation energies in kcal per mole derived from the grain boundary relaxation phenomena are 34.5 for aluminum, 73.5 for nickel, 31.5 for copper, and 41.5 for silver. It was found that the rain boundary relaxation strength in these metals increases with the reported stacking-fault energy. GRAIN boundary relaxation phenomena have been observed in a large number of polycrystalline metals and alloys. Numerous investigations have been conducted to study the structure of the grain boundary through this relaxation process. One of the first investigators was Ke1-4 who observed that the activation energy for grain boundary relaxation in aluminum, a brass, and a iron was about the same as that for volume diffusion. He concluded that the grain boundary behaved as if it were a thin liquid layer with neighboring grains sliding over one another. Leak5 conducted experiments on iron of a higher purity and observed that the grain boundary activation energy is comparable with that of grain boundary diffusion. He suggested that, in metals where this relationship holds, the damping may be caused by a reversible migration of grain boundaries into adjoining grains. Nowick6 has presented an interesting view of inter-facial relaxation with his "sphere of relaxation" model. A relaxed interface is represented as one where the shear stress is greater than the normal value along the edges and zero in the interior of the interface. The region of the stress relaxation is pictured as a sphere surrounding the interface. From his calculations Nowick concluded that the slip along an interface is directly proportional to its length. Therefore, the time of relaxation, T, depends on the size of the relaxation interface. This means that in the Arrhenius relationship, t = TO exp[H/RT], valid for atom movements, the relaxation time T is predicted to be proportional to the grain diameter through the pre-exponential term, TO. Since the internal friction can be given as Q-1 = ?j wt/(1 + w2r2), where ?J is the relaxation strength and w is the angular frequency, an increase in grain size at a constant frequency will shift the peak to a higher temperature. A great deal of work has been done to determine the exact relationship between the internal friction and grain size.1,5,7,8 In metals, the grain boundary peaks are found to be lower and broader than predicted theoretically.' The above model can explain this by a distribution in the size of the interface areas, represented by a distribution in the parameter tO, and an overlap of spheres of relaxation, represented by a distribution in activation energies. Both these phenomena result in an over-all distribution in the relaxation time, which could affect the internal friction peak height, breadth, and also position. This relationship between the experimental data and theoretical calculations appears very promising in the study of interfacial relaxation mechanisms. THEORY A lognormal distribution in t can sometimes be used to adequately describe the spectrum of relaxation times governing an anelastic relaxation. wiechert9 originally suggested such a distribution to explain the elastic after-effect in solids. This choice is particularly applicable to grain boundary relaxation when considering Saltykov's work.'' He found a lognormal distribution in the grain sizes within a metal. Recently Nowick and Berry11 have introduced a log-normal distribution in T into the theoretical internal friction equations. The form of the distribution function is where z = In(r/rm), and Tm is the mean value of t. The parameter ß is a measure of the distribution and is the half-width of the distribution when is l/e of its maximum, IC/(O). Nowick and Berry have described the methods to obtain the parameters Tm, ß, and ?,J from experimental internal friction and creep test data. In the idealized case, where only one relaxation event occurs with one relaxation time, only ?J and T are necessary to completely describe the event, and 0 = 0. For the broader internal friction curves 6 is some positive number greater than zero. The larger the 6, the greater is the half-width of the distribution in In t.

Jan 1, 1967

By Emmanuel P. Papadakis

Ultrasonic velocity measurements have been made to study the preferred orientation in cube-textured copper. Methods applicable to thin specimens were employed since the specimens were necessarily of sheet material. The measured velocities in various directions in the sheet differed from the corresponding values in single-crystal copper by 1 to 6 pet. The distribution of the deviations indicated that the align-ment of the (001) planes with the rolling plane was better than the alignment of the [100]and [010] directions with the rolling and transverse directions. Ultrasonic pole figures (velocity us orientation) are shown to be useful in the study of preferred orientation. THIS paper describes one set of experiments in a continuing study of preferred orientation in worked metals. This study has been undertaken to investigate the fundamental properties of metals when used as propagation media for ultrasonic waves. Many such materials are of current or potential use in ultrasonic delay lines. Fundamental studies on ultrasonic propagation parameters such as velocity, attenuation, and diffraction (beam spreading) are of importance in the design of delay lines, in the development of nondestructive testing methods, and in the study of materials themselves. Preferred orientation in worked poly-crystalline metals influences all three above-mentioned parameters, and hence is of particular importance. When polycrystalline metals are subjected to mechanical working, they develop textures dependent upon their crystal structure and the symmetry of the working operation.' The texture consists in the alignment of the crystallographic axes of the grains in preferred directions with respect to the symmetry axes of the working operation. Since the grains are elastically anisotropic, the elastic moduli of worked metals are anisotropic. Hence the velocities of elastic waves in worked metals depend on the directions of propagation and polarization. The worked metal may be thought of as taking on the elastic symmetry of a single crystal: so it possesses the same number of independent elastic moduli as the crystal class it simulates. In general, a worked metal does not adopt the crystalline symmetry of its own grains. For instance, most rolled sheet becomes effectively orthorhombic while all bar stock and wire develop hexagonal symmetry. However, certain metals with cubic crystal structure develop a cube texture upon rolling and annealing.= Nearly perfect alignment of [100]-type directions with the rolling direction, transverse direction, and rolling-plane norma1 can be achieved in certain fcc metals and alloys. These cube-textured rolled metals provide an excellent opportunity to test preferred orientation by means of elastic waves, since a worked metal with 100 pct cube texture would have elastic moduli identical to the moduli of its constituent metal. It is the purpose of this paper to present the results of an investigation upon cube-textured copper. Ultrasonic waves were used. The methods of measurement and the experimental results on the effective moduli will be given. The ultrasonic measurements will be shown to complement X-ray pole figures for the determination of preferred orientation in worked metals. EXPERIMENT To study cube - textured material, it was necessary to use thin-sheet material since a severe reduction in gage (95 to 99 pct) is necessary to produce cube texture. Special ultrasonic methods were needed to investigate the thin material at megacycle frequencies. A) Materials. The cube-textured material tested was a copper alloy containing 1 pct Zn. Specimens already measured for Young's modulus4 by Alers were kindly supplied by him. The specimens were slabs 3.00 by 0.25 in. cut from sheet 0.047 in. thick. The orientations of the long axes of the specimens with respect to the rolling direction were taken in 15-deg steps from 0 to 90 deg. B) Measurements. Two distinct experiments were performed to measure the phase velocity in these specimens. One measured the shear wave velocity for propagation in the 0.25-in. direction and polarization in the 3.00-in. direction. The other measured the velocity of both shear and longitudinal waves propagating in the thickness direction in the sheet. 1) Plate-Mode Measurements. The velocity of the zeroth-order shear mode5 was measured in the 0.25-in. direction in each strip. The specimens were ground thinner over half their length to assure that the first-order shear mode would be cut off below 6 Mc per sec, leaving the zeroth-order nondispersive shear mode as the only propagating mode. Piezoelectric ceramic transducers of 5 Mc per sec resonant frequency poled in their long direction were solder-bonded to the edges of the thin part of the slabs as in Fig. 1 after these edges had been made flat and parallel by fine grinding. These transducers produced waves polarized in the 3.00-in. direction and propa-

Jan 1, 1967

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By G. E. Wittur

"The twenty-one members of the Organization for Economic Cooperation and Development, comprising eighteen western European nations plus Canada, the United States and Japan. account for two-thirds of world steel production. The Special Committee for Iron and Steel was formed by the OECD to study trends and problems in the steel industries of member countries. The paper begins with a summary on the Organization, including an historical sketch, its structure, member-ship and objectives. The steel industry of the entire OECD is briefly described before proceeding to a more detailed discussion of various aspects of the steel industries of European OECD members, emphasizing practices and conditions that differ from those in North America. Benefits to Canada of representation at meetings of the OECD Special Committee for Iron and Steel are described."

Jan 1, 1967

By M. A. Upham

"MINING is Canada's second largest basic industry, producing material with a gross value of 2.5 billion dollars, led only by agriculture with 2.9 billion dollars. It pro-vides employment, directly and in-directly, for three quarters of a million people. Since the Second War, the value of mineral production in Canada has tripled. Economists forecast that over the next 15 years its value will triple again. Canada is a basic and leading supplier of nickel, iron, copper, zinc, lead and uranium. It is also a major oil producer, leads the world in the production of asbestos and in five years will be the leading producer of potash, a basic constituent of fertilizer.It can be seen that Canada's wealth and economic progress lies in being a primary producer of economic minerals and in building secondary industries to manufacture finished products from these raw materials. Canada's future in the field of mineral production looks bright, with our resources just starting to be tapped. Outside of the large expanse of Soviet Russia, we are by far the world's most fertile mineral exploration area."

Jan 1, 1967

By M. C. Makepeace

"It is the objective of designed experiments to obtain more information for less material and process cost than can be obtained by traditional experimentation. In this paper, the fundamental concepts on which the statistical design of experiments is based are briefly re-viewed according to the following outline: The Experiment The Design The Analysis Two simple 2"" factorial experiments are presented as examples."

Jan 1, 1967

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll' pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,''' and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.'-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By J. P. Morris

The Bureau of Mines investigated the mechanics of fuming of iron-carbon melts during top-blowing with oxygen. Melts weighing 45 lb were prepared in an induction furnace and blown with oxygen by means of water-cooled lances. The rate of fuming was measured and correlated with the operating variables. The data showed that the primary cause of fuming was a boil at the bath surface in the impingement zone of the oxygen jet. Nucleation of the carbon monoxide bubbles producing the boil was apparently brought about by the precipitation of an oxide phase. The actual fuming mechanism involved partial oxidation and vaporization of bubble films and fine metal spray generated by the bursting of the bubbles. Bubbles that formed outside the impingement zone produced little fume. The distribution of trace elements between the metal and fume strongly indicated that the fume contained fine spray particles as well as particles that had condensed from vapor. The rate of fuming was found to be proportional to the carbon content of the metal) the concentration of oxygen in the jet) and the bath temperature) provided that a continuous boil occurred. In the absence of a boil) very little fume was produced.

Jan 1, 1967

By Bernard Porter

The rate of the heterogeneous reaction between reactor-grade yttrium and lithium fluoride in lithium fluoride-yttrium fluoride mixtures was measured using a quartz spring balance. At 950° C the magnitude of the rate of reaction is 10-5 grams of yttrium/cm2-sec. The heat of activation for the reaction is 38.3 kilocalories per mole of LiF. A surface-controlled mechanism is proposed in which LiF is adsorbed on the yttrium metal surface. An activated complex is formed when additional LiF reacts with the adsorbed LiF-metal site. The activated complex then decomposes to the products) which are lithium metal and YF3. The importance of the reaction in the electrowinning of yttrium metal from fluoride electrolytes is discussed.

Jan 1, 1967

By Maurice Lauzon

"Aerial surveys of the open pits have been conducted regularly at Lake Asbestos of Quebec, Ltd. -a subsidiary of American Smelting and Re-fining Company -since 1958. Ground controls are supplied by Lake Asbestos, and a topographic map of the pits at a scale of 1 in. to 50 ft., with 2-foot contour intervals, is obtained by aerial photography. The information from the topographic map is then transferred by the Lake Asbestos engineering staff to sections from which the volumes removed are calculated. Considering the size and complexity of the operation, this system has proved to be the cheapest, fastest and most accurate way of determining the quantities of rock and overburden removed. More than 11,000,000 tons of ore and waste are mined each year in three different pits. Further-more, the nature, shape and extent of the orebodies make it necessary to mine on many (up to eight) benches of a pit during a single year. In addition, there are sections of the pits where it is impossible or un-safe to survey the crest of some benches by standard ground methods. For these reasons, the tonnages obtained by truck count are checked and adjusted by aerial survey. These surveys are now taking place every six months. With this system, it is possible for a two-man surveying crew to look after all field work in the mine area."

Jan 1, 1967

By C. E. Coleman, D. Hardie, A. E. Wraith

A photoguaplric method of measuring crack velocities has been applied to an examilzation of- the effect of hydrogen on the impact properties of zirconium. Results indicate that the crack in hydrided zirconit travels at about 26 m per sec whereas that in the uacuum -annealed is dependent on the speed of the hammer. RECENT work on the effect of hydrogen on zirconium reveals that when hydrided zirconium is tested in slow bending the crack producing failure can be unstable. The mode of fracture seems to involve the crack linking up broken hydrides by a ductile mechanism in the zirconium matrix.2" In order to compare the fracture of zirconium with that of other metals which show unstable crack propagation, notably steel, the rate of the crack spread must be known. As the methods previously used for measuring crack growth are either unsuitable for the present work5-'' or very costly," a simple technique has been devised in which the maximum crack velocity is derived from a series of crack position-time measurements. EXPERIMENTAL PROCEDURE The experimental arrangement is shown schematically in Fig. 1. The flash unit12 was triggered when the Charpy hammer touched the specimen and the 6-psec flash of the lamp delayed by a preselected time interval in the range 100psec to 10 msec. The camera was left on open shutter during the test. From direct measurement on a calibrated photographic print, Fig. 2, the position of the crack and the specimen was found at a known time after impact and, from a series of such tests using an appropriate range of flash-delay times, the crack velocity was estimated. Preliminary experiments were carried out on mild steel above and below its transition temperature. Vacuum-annealed zirconium, and zirconium hydrided to 100 ppm H were then tested at 20" and 150°C. For comparison, Zr-2.6 pct Nb alloy (in the 0 + transformed /3 condition), vacuum-annealed or hydrided to 100 ppm H, was tested at 20 C. The chemical analyses of these materials are given in Table I. For the high-temperature tests a fine chromel-alumel thermocouple was spot-welded onto each specimen close to the notch. The test piece was heated up to 200°C to allow enough time for preparing the apparatus while the specimen cooled to the testing tem- perature. It was assumed that the specimen cooled uniformly. The accuracy of the flash-delay time was better than i2 pct i 5 psec. The crack length was taken as its maximum distance traveled normal to the length axis of the specimen. Errors in these measurements arise as a result of the uncertainty in the location of the crack tip and the difficulty in defining the exact position of the crack starting point. The latter was due to the bonding and large amounts of deformation at the hammer contact point, especially in the vacuum-annealed specimens tested at 150°C. The maximum error in the measurements was however estimated to be about 5 pct. DISCUSSION OF RESULTS From the trial experiments using mild steel above its transition temperature it can be seen from the plot of crack length against time after impact, Fig. 3. that a reasonable estimate of the maximum crack velocity at the surface of the specimen may be made. Other features of note are the initiation time before the crack is first seen and the slowing down period

Jan 1, 1967

By A. Balint

The Photometric Optical Separation process is introduced and examples of sorting machines are given. Applications of the process are outlined in general terms with reference to specific types of industrial installations. Brief description is given of the capabilities and limitations of available equipment, including cost estimates.

Jan 1, 1967

By W. C. Maurer

Although millions of feet of rock are drilled annually, the basic drilling mechanisms involved are not well understood. The primary reason for this lack of knowledge is because the basic principles of rock failure are not well understood and rock failure is the primary mechanism in drilling. A better understanding of the drilling mechanisms would enable a more scientific approach to the design and use of drills and bits. The paper reviews several models which have been proposed to explain various aspects of the different drilling methods. These models are described and their limitations and areas of application are discussed. Drilling rate relationships are developed and related to the basic rock failure mechanisms. TYPES OF MECHANICAL DRILLS There are three basic methods of mechanically attacking rock: 1) percussive action, 2) rotary action, and 3) combined rotary-percussive action. A percussion drill applies a force perpendicular to the rock surface and the bit moves into the rock perpendicular to the surface, forming a crater beneath it (Fig. 1). A rotary drill applies a constant thrust to the bit while a torsional force moves the bit parallel to the rock surface, breaking the rock ahead of it. A rotary-percussive drill applies both a rotary force and a percussive force to the bit which moves into the rock at an angle to the surface. The commonly used drills can be classified as: rotary-drag, diamond; percussive-hammer, piston, churn; and combination-rotary-percussive, roller.

Jan 1, 1967

By H. Bartholomew, L. Bernstein

Experirmental bonds of Ag-In SLID to gold, copper, nickel, Kovar, Dumet, nickel-plated molybdenum, ALL-Pt vrzetallizing on ceramic, and nickel-plated Mo-Ti metallizing on Al2O3 ceramic have been made and exalnined. Metallographic taper sections were made of all bonds for Phase identification. In addition, failuve temperatltres were determined for bonds heated undev shear load. Sowe bonds were subjected to electvon-probe microanalysis. The ternary SLID system Ag-In-Sn was similarly evaluated. Plwtonticrogaphs and electron-probe data are discussed and related to over-all phase diagrams , diffusion effects, and wetting properties of the liquid. The rates of diffusion andor compound formation of gold, silver, and copper in indium and In-Sn liquids are found to descend in that order, as measured by the relatzve thickness of phase layers in the interfaces of bonds made at 200to 400°C. It is concluded that the SLID process enables one to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures, and meet most requirements for application in interconnection, silicon bonding, or hermetic sealing of electronic devices. In a previous publication by one of the authors, the theory and principle of SLID bonding in simple binary systems was discussed. SLID bonding can be defined as a joining process using a preform with a laminated structure: a low-melting material clad on a high-melting core. During the bonding cycle a metallurgical transformation occurs such that the resultant structure can withstand, without reliquefying, temperatures higher than those at which the bond was made. The phases present in the joint interface region are high-melting compounds or, if equilibrium is reached, solid solution. Properties will depend on the phases present, ultimately approaching those of the solid substrate core of the SLID preform. The high-temperature strength of bonds made in these systems was correlated to phase identification in the interfacial bond regions from metallographic cross sections and electron-probe X-ray microanalysis data. When complex electronic components are assembled, multiphase systems result at the interfaces of bond regions. In these ternary and higher-order systems very little diffusion and phase-diagram data is available with which to predict the nature of the interfacia1 region that will result from conventional fabrication processes and subsequent field use of the component. Clarke and Rhines did early work in the field using the Al-Mg-Zn system as a vehicle. Guy and co-workers studied a portion of the Cu-Zn-Ni system and some mathematical4 and general5 aspects of multiphase diffusion. irkald' and coworkerse recently studied diffusion in the Cu-Zn-Sn system. No diffusion studies have been made on ternary systems directly applicable to this investigation but some phase diagrams are available: g-u-n, u-i-n, and CU-i-n. I) DESCRIPTION AND EXPERIMENTAL PROCEDURE The elements Au, Ag, Cu, Ni, In, and Sn are found in alloy systems commonly used in fabricating and assembling electronic components. Reference to the appropriate phase diagrams9 and the previous publication will indicate that the binary systems of any of the two low-melting elements, indium and tin, with any one of the other four higher-melting elements are capable of producing SLID bonds. It is not unreasonable to assume that any ternary or higher-order alloy system containing at least one of the elements gold, silver, copper, or nickel and one or both of the elements indium and tin could be used to produce bonds which are stable at high temperatures, after having been fabricated at low temperatures. Indeed, the liquidus contours and isothermal sections of those phase diagrams available7 do so indicate. The parameters affecting the bond and the equipment used in evaluating the bond were described in an earlier paper.' The current investigation used the

Jan 1, 1967

By John S. Berber

To improve the economics of low-temperature carbonization of coal, the Bureau of Mines is conducting research on the upgrading of the product tar to marketable chemicals. This report describes experiments on the catalytic hydrodealkylation, followed by catalytic vapor-phase oxidation of the dealkylate to phthalic and maleic anhydrides, of mixed residues from the urea adduction of lignite-neutral oil fraction and on the catalytic thermal dealkylation of high-boiling tar acids. The hydrodealkylation experiments were conducted at pressures from 1,000 to 1,750 psig and at temperatures from 600° to 1,000° F. The oxidation was, in all cases, at atmospheric pressure and 9500 F. Maximum yield of maleic anhydride, based on the liquid feed to the hydrodealky1ation unit, was 12.2 percent at 750° F and 1,500 psig; that of phthalic anhydirde was 6.9 percent at 650° F and 1,500 psig. Maximum yield of combined anhydrides was 18.8 percent at 650° F and 1,500 psig. The non-dealkylated feed material, upon oxidation, yielded 8.9 percent and 3.8 percent maleic anhydride and phthalic anhydride, respectively.

Jan 1, 1967

By David B. Brooks

I gratefully acknowledge the help of a number of American and Canadian geologists, in both federal surveys and in private firms, who took the time to discuss this problem with me. Hans Landsberg and Bruce Netschert also followed the study with interest and encouragement. 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.1/ 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 vest 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.? 2/ 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.

Jan 1, 1967

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar' in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.' Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,' be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,'' however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By Joseph M. Singer

Having established that sodium chloride reduces the incendivity of explosives, the Bureau of Mines studied the effect of sodium nitrate in reducing ignition hazards. Gallery experiments showed that sodium nitrate reduced the incendivity of certain explosives to 8 percent natural gas in air but increased their incendivity to coal dust predispersed in air. Laboratory experiments using hot jets from explosions of stoichiometric mixtures of methane-oxygen-nitrogen showed that both sodium chloride and sodium nitrate reduced the incendivity to methane, to mixtures of coal dust and methane) and to coal dust. The difference between the gallery and laboratory results with respect to coal dust is attributed to temperature-time effects.

Jan 1, 1967

By G. H. Charlewood, J. W. McBean

"One hundred years after being developed, the diamond drill is still an essential tool in mineral exploration. The basic principle is unchanged, but the technique has been revolutionized, particularly in the past fifteen years. The cost of core drilling has not kept pace with the rising cost of living. The price of machinery, supplies and labour in drilling has doubled and trebled since 1946. Some of the techniques which have made it possible to hold the price line are described."

Jan 1, 1967