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By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By C. A. Stickels

In a recent paper, Held1 showed that rolling conditions can have a marked effect on the volume fraction of surface texture produced in low-carbon steel. This variation in rolling texture is reflected in the recrys-tallization texture and affects the plastic properties of the annealed sheet. The fact that roll friction can influence the surface deformation texture in iron and steel has been known for some time;'= but the magnitude of the effect has never been shown quite so clearly before. The analogous effect during wire drawing has been recognized for many year.4 Dillamore and Roberts5 examined surface textures in warm- and cold-rolled aluminum and copper. They found that when a surface texture was present it could be described as the interior texture rotated about the transverse sheet direction. The angle of rotation was a function of the type of lubrication, the amount of reduction per pass, and the temperature of rolling. The purpose of the present note is to show that surface textures in cold-rolled iron can also be described as interior textures rotated about the transverse sheet direction. Vacuum-melted electrolytic iron* was straight- rolled 90 pct at room temperature in a two-high rolling mill with 5-in.-diam rolls. Two rolling procedures were used: a) no lubrication with reductions of about 0.035 in. per pass, and b) heavy lubrication with lano-line and reductions of about 0.002 in. per pass. The final sheet thickness was 0.030 in. (110) pole figures were determined by transmission through specimens taken from the sheet surface and sheet midplane. The surface texture of the sheet cold-rolled according to procedure a is shown in Fig. l.* The shapes of the low-intensity contour lines indicate that the texture can be described as a partial fiber texture with a (110) fiber axis normal to the sheet. The approximate range of orientstions present is (011)[211] — (0ll)[100] — (011)[211]. This range of orientations is what one would obtain by rotating the interior texture 90 deg about the transverse sheet direction. The intensity of (110) and (222) reflections from planes parallel to the surface was measured after removing metal from the surface by chemical polishing. The surface texture here was confined to the outer

Jan 1, 1968

By Erwin L. Zodrow

"This paper is based on a statistical analysis of the Smallwood iron ore mine (6). In this mine, the prediction of magnetite is especially difficult because of strong trends. Recognizing the statistical limitations of the sample data, the paper approaches the basic statistical analysis of the magnetite by endeavouring to obtain a first approximation of its sample density function. The knowledge of the distribution of a random variable is essential for several reasons, but particularly: (1) to obtain reliable estimators of the population parameters -for example, mean and variance; and (2) to use these estimators in hypothesis-testing concerning future experiments -sample points and sample intervals."

Jan 1, 1968

By J. Tuzo Wilson

"AT ANY TIME, it is a pleasure to me to be invited to address The Canadian Institute of Mining and Metallurgy because it represents an industry and men with whom I have been happily, if peripherally, associated continuously for forty years. This year, it is a particular pleasure because I believe that an important subject has arisen which I propose to discuss.This is a major discovery in the earth sciences, first fully revealed this winter, but already widely accepted. The basis of this revolution, for it is no less, is that measurements of three different features of the earth all change in exactly the same ratios. These ratios are the same in all parts of the world. The results from one set are thus being used to make precise numerical predictions about all the sets in all parts of the world. No such accurate correlations and predictions have ever been found before in geology or areal geophysics. The whole subject of earth science has thereby been radically altered.The first of these measurements is that of the direction of magnetic polarity in lava flows. When piles of young lavas are examined with the aid of a pocket compass, it is noted that some flows are magnetized in the direction of the earth's field and some in the reverse direction (Figure 1). By accurately dating enough flows, a time scale of the dates of reversals has been established. During the past four million years, nine reversals have occurred synchronously all over the world (Cox, Darymple and Doell, 1967, McDougall and Chamalaun, 1966) (Figure 2). It appears that the scale can be extended back to Precambrian times (McMahon and Strangway, 1967). This time scale is the first of the 'three identical ratios."

Jan 1, 1968

By John J. Dwyer

As one begins to contemplate the organization of a talk with the title "Iron Ore - The Permanent State of Evolution," the main divisions appear to be the past, the present, and the future. But distaste for repetition of the present production achievements, which scarcely need additional description on this occasion, soon leads one to the conclusion that a more appropriate division of the subject is simply the past and the future . . . with emphasis on the future. We are working in the present, but it can only be understood by what has taken place in the years and decades gone by, and/or under what terms we will have to face the future. Evolution is more often thought of as a steady change - but steady change is really the product of revolutions, sometimes making headlines but often unnoticed at the time. With hindsight, we recognize the great importance of the emergence of the Bessemer converter and the open hearth and the vast influence that both have had on steel making and the changing ore demand. In this country we also see schooners opening the era for lake transportation of iron ore from Michigan to Take Erie. Later, steamships haul the ore from the Mesabi Range to the steel centers of the country. In order to take full advantage of the inland seaway, there had to be revolutions in ship design, loading and unloading facilities and channel and lock development. Full scale utilization of the resources of the Mesabi Range, itself, required parallel upheavals such as the development of new production equipment, and substitution of modern forms of energy for horsepower, and, yes, manpower, as well.

Jan 1, 1968

By Charles C. Peterson, Ronald E. Enstrom

Significant improvements have been made in the ursine systern for epitaxial vapor gvowtlz of Gds. The electron concentration has been reduced to below 1015 cm-3 with electron-mobility values as high as 7200 sq on per v-sec at 30PK and 60,000 sq cw7 per v-sec at 77°K. These high-purity layers have been successfully gvown on n&apos; layers with thicknesses as snzall as 1 p and as large as 125 p. Furthermore, high-purity layers have been incorporated into an structure without degradation of electrical properties. Different impurity gradients at the n&apos; to n interface were achieved. Using these structures, Gunn oscillators have been operated at frequencies as low as 0.4 GHz and as high as 40 GHz, which equals the highest valzle yet reported. The frequencies nleasured are in reasonable apeenlent with those calculated fron7 the n-layer widths and the transit times. CW operatiolz has been achieved from 3 to 20 GHz. In Gunn devices for >40 GHz operation (i.e., witk an n-layer tkickness below 2.5p), the n layer has been generally too pure to permit oscillations to occuv. ThE mechanism of the Gunn oscillator&apos; is now generally understood.2-5 Electron transfer from the (000) minimum to the ( 100) minima leads to a voltage-controlled negative resistance, which results in the formation of domains of high and low electric fields which travel through the crystal with a characteristic velocity of about 107 cm per sec. When a constant voltage is applied to the sample, this domain motion generaliy leads to oscillations at the transit time frequency, fT = 107/L, where L is the thickness of the active n layer.&apos; In this case, a single high-field domain is nucleated at the cathode and grows until it reaches the anode, where it is absorbed; a new domain then forms at the cathode.5 There are related modes of oscillation of the same device in which a tuned circuit causes a periodic variation of the voltage across the device. The frequency then may be either above or below fT. It has been shown that oscillations will occur when n • L 2 1012 cm"2, where n is the carrier concentration in the active region. At lower doping densities, 10" 5 n . L 5 lo&apos;&apos;, the doping is said to be subcritical for oscillation and the description of the device operation changes since the domains become comparable in thickness to the device thickness, L. Nevertheless, such devices have been found to be "active" and, in fact, are useful as amplifiers.778 For CW operation, one wishes to minimize the power dissipation, which is related to the electric field, E, and the low-field resistivity, p. Below threshold, the power dissipation density is approximately Typically, at threshold where E -- 3 x 103 v per cm, the dissipation density is 107/p watts per cu cm, p in ohm-cm. Furthermore, it is desirable to provide good conduction of the heat generated in the active region. The temperature rise, AT, across the active layer of a sandwich structure, with a heat sink on one side, is given by AT = (E&apos;/P)(L~/~~) where it is assumed that the thermal conductivity, u, and resistivity, p, of GaAs do not vary appreciably over the range of temperature and electric fields existing in the layer. This expression shows that, subject to maintaining an appropriate (n . L) product, CW operation is favored by a higher resistivity, a lower threshold field, and a thinner device. The above device requirements place some severe restrictions on the materials to be used, especially for high-frequency (>10 GHz) operation. Here, it is necessary to prepare very thin (<10 µ) layers of GaAs, in a state of high purity (-1 ohm-cm), complete with very low-resistance ohmic contacts. Problems of handling such thin and fragile samples become inereasingly severe as the frequency is raised. Furthermore, while good low-resistance ohmic contacts are easily applied to low-resistivity GaAs, contacting difficulties are encountered for these higher-resistivity materials.

Jan 1, 1968

By R. W. Sayers

The Duval Corporation porphyry copper deposits at Copper Canyon and Copper Basin, though widely separated, form an economic unit requiring integrated exploitation. Contrasts in mineralization, host rocks, and mode of occurrence present unique mining and milling problems. Mixed oxide-sulfide ore is treated in extensive dump leaching facilities in both areas. Complex copper-gold-silver ore is treated in a 4,000 tpd mill at Copper Canyon. In both areas, hypogene metallization occurs within large aureoles of metamorphism and hydrothermal alteration related to quartz monzonite intrusions of mid-Tertiary age. Supergene processes further altered the rocks and enriched the hypogene protore. At Copper Canyon, hypogene copper and iron sulfides with gold and silver occur in fractures, as partial replacement of favorable beds, and as disseminations in Paleozoic sedimentary rocks. The lower part of the Pennsylvanian Battle Formation was a particularly favorable host. Metallization occurs to a lesser extent in quartz monzonite. Metal zoning is well developed. The deposits at Copper Basin consist principally of supergene copper minerals in arenites of the Cambrian Harmony Formation. Oxidation of hypogene copper and iron sulfides in tactite zones has formed at least two commercial deposits; intersections of fractures with favorable beds exerted important ore controls.

Jan 1, 1968

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.&apos; The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8&apos;10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.&apos; It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1&apos;2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968

By G. W. Toop

In a recent publication,31 Darken has derived an equation to describe thermodynamic behavior in ternary metallic solutions with compositions near pure component 1: Eq. [I] is understood to be a general equation, consistent with the ternary Gibbs-Duhem equation, which is proposed as a logical formalism in view of observed behavior in some binary metallic solutions31&apos;32 rich In Eq. and am are constants obtainable from the 1-2 and 1-3 binaries. The parameter 023 may be determined from measurements on the ternary The purpose of this discussion is to compare Eq. [I) or [3] with other ternary formulations involving binary terms, within the regions of validity of Eqs. [I], [2], and [3]. First, the ternary point is considered to be at the intersection of two composition paths, one with constant N1 and another with constant N2/N3 as shown in Fig. 10. The terms in Eq. [3] may be related to the binary points shown by multiplying the first term on the right-hand side of Eq. [3] by N2 (1) /l -N1, the second term by the third term by and the fourth term by each multiplier being unity: It should be noted here that no suggestion has been made that either the binary or the ternary systems form regular solutions. However, Eq. [5] and hence Eq. [3] shows that the contribution made to the ternary excess free energy from the 1-2 and 1-3 binaries has the same form as for a regular ternary system.1 Before considering the term a23 for the above case, a second geometrical relationship is examined with the ternary point at the intersect ion of three composition paths with constant N1/N2, N2/N3, and Nl/N3, respectively, as shown in Fig. 11. For this geometry, ternary values of NZ and N3 in terms of the binary values shown may be substituted into Eq. [I]. Then by making use of identities of the form Eq. [6] contains terms that are similar to those in a ternary regular solution formulation34 based on the geometry shown in Fig. 11. Although at finite concentrations, unless the 1-2 and 1-3 binaries form

Jan 1, 1968

By C. W. Eggert

"The idea for this talk came to me last year when I was attending the Canadian Gold Metallurgists Meeting. I talked about it to a friend of mine who is an authority on mineral dressing, particularly the theoretical end of the business. He remarked that this was an excellent technical note, why don't you write it up. This is what I have for presentation this morning. I hope in presenting this type of idea in this way it is in keeping with the tradition of the Canadian Gold Metallurgists which was to function on a not too sophisticated level and where operators could get together and trade ideas in an informal way.My basic thesis is that it should be possible to evaluate screen analyses by the application of the standard statistical probability theory. In any statistical analysis the sample is the first consideration. If we look at existing methods of size evaluation we find it is usually based on the fact that a given particle will pass one square aperature and not another. One system of standardizing how these aperatures will be set up is based on Rittenger' s work with the ratio of hole sizes proportional to the square root of 2. Keeping in mind the limitation we have accepted this as our method of 11 sizing"" in attempting to apply standard statistical methods to screen analysis."

Jan 1, 1968

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-&apos;, a lo-&apos;-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10&apos; cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell&apos;s law that where = critical angle, n - index of refraction of air, n&apos; - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,&apos; and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert&apos;s law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

By F. G. Miller

To improve coal flotation Bethlehem Steel Corporation&apos;s Research Department has been working on a number of related problems based on both physical and chemical factors. The ideal is of course full understanding of the interrelated effects of both sets of factors. However, detailed studies5 of each physical factor have produced immediately usable results in commercial coal flotation and are providing the bas is for our current work on the effect of chemical factors. Since these detailed studies provided the basis for the present investigation of froth sprinkling, their key results are highlighted here. For example, for a highly floatable bituminous coal, particle floatability was shown to be directly related to the percentage of coal surface available for bubble attachment and inversely related to particle mass. The data also underscored that in a given size range the addition of mineral matter to a particle makes flotation more difficult both by adding to the mass of the particle and by decreasing the amount of coal surface available for bubble attachment. Size also affects particle floatability in that as the size of particles of a given specific gravity increases, mass increases and the ratio between coal surface area and mass of the particle decreases. Flotation tests showed that any recovery of the coarsest particles in a coal feed is accompanied by progressively higher recovery of finer and finer particles. Consequently, fine high-specific-gravity particles are recovered with the coarse good coal. As a result, when the entire 14M x 0 size range is processed by froth flotation, the good coarse coal is contaminated with high-specific-gravity fines. It is the small quantities of these fines that must be rejected from the froth product if flotation efficiency is to be increased above its present level.

Jan 1, 1968

By I. M. Bernstein

The steady-state creep behaviov of zirconium and zivcaloy-2 was examined in the temperature vatlge 520° to 620°C A1 low stresses the creep rates were cimracterized by a linear stress dependence; at highev stresses the stress dependence was much more pronounced. Temnperature-cycling tests yielded values for the aclivation enevgy for creep. Various tlzeories were examined in the ligltt of- the experimental re-sults and it mas concluded that the low-stress creep behavior is the result of the stress-direcled diffusion of vacancies along gain boundaries. It has been observed,"&apos; usually under conditions of high temperature and low stress, that creep deformation can occur for which the steady-state creep rate is linearly dependent on the applied stress. For magnesium and certain magnesium alloys, Harris and ones&apos; and ones&apos; have argued that this type of creep occurs by mass transfer as a result of the stress-induced generation and migration of vacancies, along a gradient defined by the stress direction. Jones&apos; demonstrated that the rate-controlling diffusion path is sensitive to grain size and temperature, and that by suitable control of these variables creep could occur by vacancy diffusion either predominately along grain boundaries or through the lattice. Recently, Jones3 suggested from an examination of limited high-stress data for zircaloy-2, composition in Table I, that significant diffusion creep could occur at low stresses, at least between 375" and 500°C, controlled by grain boundary vacancy diffusion. This process could have an important implication in assessing the role of zirconium alloys as a structural or cladding material in certain classes of nuclear reactors, since it predicts creep deformation far in excess of any estimates based on extrapolating slip creep data from higher stress levels. If the diffusion creep process occurs it should be possible to describe the total steady-state creep rate of zirconium and its alloys as the sum of two terms, Eq. [I]; the first term relates to a slip creep process important at high stresses and which is manifested by a much more pronounced dependence of creep rate on stress4 than diffusion creep and the second to a process controlled by mass transfer,5&apos;6 dominant at low stresses: where A and BI are parameters which can depend on structure, Ql and Q2 are the activation energies for the particular creep process occurring, and n describes the sensitivity of the creep rate on stress. It is the purpose of this paper to present some direct experimental evidence in support of this view. It is recognized that other analytical approaches have been proposed to explain data of this kind and these will also be discussed. 1) EXPERIMENTAL PROCEDURE Flat creep specimens (gage length 1 by 0.25 by 0.02 in. approx) were prepared from cold-rolled, argon-remelted, crystal bar zirconium and cold-rolled commercial-grade zircaloy-2, the analyses of which are given in Table I. The specimens were annealed at a pressure of < 10-5 Torr at temperatures from 625" to 675°C for 2 hr and slow-cooled. This treatment produced stable grains of average size (defined here by the average linear intercept) of for zirconium and -4xin. (-10 p) for zircaloy-2. The specimens were tested in a dead load tensile creep rig. The stress was maintained constant by adjusting the applied load after approximately each 1 pct of strain. The specimen temperature was controlled to better than +1°C. This system had a small thermal lag, so that rapid temperature changes were possible. To minimize corrosion, the specimens were tested in high-purity (99.95 pct) argon, further dried,

Jan 1, 1968

By H. I. Kaplan, C. Laird

Pulsating contpresslon experiments have been carried out on coppev single crystals in order to test the adequacy of mechanisms which have been suggested for stage I cvack grouth when tension-compression loading is the mode of- applying stress. Although dejorrrzation continues slowly for many millions 01 cycles under Pulsating compression stresses both within slip bands formed in the first cycle and by the creation of new bands, the morphology of these bands is not typical of fatigue slip bands in general and neither initiation of cracks nor propagation of artificially induced cracks was observed. It is therefore concluded that 1) initiation and growth of cvacks in fatigue is a consequence of repeatedly reviersed, microplastic deformation rather than intermittent, unidirectional deforma-tion, 2) gvowth of- cracks in polycrystalline specimens FAILURE of a plain specimen subjected to cyclic tension-compression stresses is known to take place by two stages of cracking.1,2 The first stage is characterized by propagation along slip planes roughly at 45 deg to the stress axis, in the outermost layers of the specimen, and at a rate of the order of angstroms per cycle. The average macro orientation of a stage I crack is normally at right angles to the stress axis,3 however, except in a few cases, e.g., single crystals in suitable orientation, when both the micro and macro directions of propagation are at 45 deg to the axis. After a stage I crack has penetrated to such a depth that the stress on the remaining section of metal is significantly increased, stage II crack propagation succeeds stage I, at right angles to the stress axis both micro and macroscopically. Direct evidence of the processes occurring during a subjected to pulsating compression stresses is caused by the setting-up of local tensile stresses due to interactions between grains, and 3) both unslipping mechanisms and operation of the "plastic blunting process " within a single slip band are adequate descriptions 01- stage I growth, being fundamentally similar. The slip mode of a material, however, is considered to control whether unslipping or the plastic blunting process takes place. Thus materials of planar slip mode fauor unslipping while those hacing a wavy mode, and capable of cross slip, can fail in stage I by the plastic blunting process. Similarly, and perhaps more importantly, reversed torsion and tension-compression modes of applying stress may be expected to cause the unslipping mechanism and the plastic blunting process, respectively. single stress cycle4,5 shows that stage II crack propagation takes place by a repetitive plastic rounding and closing of the crack tip. This mechanism has come to be called the "plastic blunting process".6 On the other hand, the extreme smallness of the phenomena occurring in stage I growth prevents elucidation of its mechanism by direct observation. Many suggestions have been proposed for this mechanism,&apos;"-" most of them involving some kind of random or systematic unslipping process. It is possible, however, that the mechanism of stage I growth is essentially the same as that of stage 11, but occurring on a much smaller scale.6 In this situation, it has been observed that cracks propagate along slip bands comprising dislocation cell structures and bounded on either side by regions of different dislocation density and distribution." Since there is evidence that such bands are softer than their matrix, * it may be expected that the plastic blunting process occurs within a single slip band during stage I growth, rather than on two gross bands as in stage 11, when the acting stress is greater.= The blunting of the crack tip allowed by coordinated

Jan 1, 1968

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968

An oxide ore heap (80,000 ton assaying 2 per cent copper) and a sulphide ore heap (300,000 ton assaying 1&#183;7 per cent copper) are being leached in series in a closed circuit system. The ore is friable and weatherseasily giving severe percolation problems. These were eased by applying liquors at 235 gal/min to trenches 2 ft wide and 6 ft deep along the full length of the heaps.Cementation recovery was improved from 20 per cent to over 80 per cent by regular intermittent agitation of the iron using a back hoe unit.Liquor pH is controlled by acid addition, and iron content is controlled by a bleed-off set according to predictions made from a pH-Eh diagram drawn for the liquor components. These controls, together with acyclic wetting and draining procedure, have raised production from 6 ton/week to 10 tdn/week of 80 per cent copper.

Jan 1, 1968

By E. A. Mihok

A pilot plant for treating mine drainage by neutralization with limestone was designed, fabricated, and operated by the Bureau of Mines. The process consists of (1) producing a very fine (minus 400-mesh) limestone slurry, (2) mixing the slurry with the mine water, (3) aerating the resulting mixture to remove carbon dioxide and precipitate iron, and (4) separating the solids from the liquid by sedimentation. A mine discharge of pH 2.8, containing 1,700 ppm total acidity, 36 ppm ferrous iron, and 360 ppm total iron, was treated at rates from 300 to 400 gpm. The treated water ultimately reached a pH of 7.4 and contained no detectable iron. The resulting sludge compacted to approximately one-third the volume of sludge from mine water neutralized with lime. The advantages of the limestone process, compared with the conventional lime process are as follows: Widespread distribution and lower cost of run-of-mine, indigenous limestone; simplicity of plant design; reduced hazards and plant operating and maintenance costs accruing from the use of a less reactive chemical agent; higher solids concentration of the precipitated sludge; and no deleterious effect caused by accidental overtreatment. While total process costs could not be determined, it is conservatively estimated that the cost of treating mine water by the limestone process is one-third to one-half the cost of the lime process, depending on the characteristics of the water to be treated and the availability and quality of limestone used.

Jan 1, 1968

By J. E. Dodge

Tasu, currently an open-pit operation, services the primary crusher from two areas by ore-pass raises. The problems encountered and advantages gained are discussed. Mine equipment and operating practices are covered, together with blasting practices, line drilling and the pre-shearing necessary to stahilize the pit walls.

Jan 1, 1968