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By W. White, C. S. Barrett, R. M. Mueller

THIS communication reports film-recorded low-energy (-100 kev) proton blocking patterns'-3 for hcp and wurtzite crystals. In particular the sequence of relative line intensities* (corresponding to planar blocking) of common hcp metals is compared with those of the wurtzite semiconductors CdS and CdSe. The results show that the sequence is characteristic of structure. For closely similar structures such as those of CdS and CdSe, differences of line intensity attributable to the difference in atomic number, 2, of the scattering centers may also be seen. The apparatus and techniques used in this work were identical with those reported previously in a study of cubic systems.3 All metals were given standard metal-lographic etches, and the semiconductors cleaved, immediately prior to introduction to the vacuum system. Fig. 1 shows the unit cell of the wurtzite structure, and the geometry used to obtain the [1120] and [0001] patterns of Fig. 2. The axial ratio, c/a, for all ma- terials of Fig. 2 is close to 1.63. The patterns are then directly comparable in linear dimensions inasmuch as they have been reproduced at the same overall magnification of the patterns. (Overall magnification is proportional to the product of film-to-target distance and printing magnification. Thus the 1/6-in.-diam beam passage hole in the center of the film need not appear of uniform size in the prints.) The patterns for a given orientation, though similar

Jan 1, 1970

By George Gauci

INTRODUCTION The Broken Hill orebody was discovered in 1883. The richness of the deposit encouraged rapid development of the field and within fifteen years ten mining companies were operating. By 1940, several companies located in the centre of the field with limited reserves, had ceased operation. These leases have been acquired by Broken Hill South Limited and North Broken Hill Limited. The four companies currently operating in the field are, in order of increasing production rate:¬- Broken Hill South Limited (BH South) North Broken Hill Limited (North BH) The Zinc Corporation, Limited (ZC) and New Broken Hill Consolidated Limited (NBHC) The tonnages treated by each company since the present plants have been in operation are shown in Figure 1. The leases are located as shown in Figure 2, and an aerial view of Broken Hill showing the spread of the City on each side of the line of lode is shown in Figure 3. The present treatment plants date back to the early 1930's when the BH South plant was built. The North BH and ZC plants were built in 1939 and NBHC's in 1952. The three plants built before 1940 have similar crushing and grinding flowsheets. NBHC differs in that it includes rod mills with consequent differences in fine crushing equipment.

Jan 1, 1970

By H. S. Price, J. C. Cavendish, R. S. Varga

This paper presents a new technique for solving some of the partial differential equations that are commonly used in simulating reservoir performance. The results of applying this technique to a simple problem show that one obtains accurate pressure values near wells, as well as accurate pressure pdients, which can be explicitly calculated. The method is completely rigorous in that convergence of the discrete numerical solution to the continuous solution for both pressure and pressure gradient is established. High-order, piecewise-polynomial approximations are used near the wells where pressure gradients are steep, while low-order, piecewise-polynomial approximations are used elsewhere to reduce greatly the calculation time. This combination is shown to give a uniformly good approximation to the solution. These approximations, obtained by using a Galerkin process with suitable Hermite subspaces, are shown to be theoretically and numerically superior to the usual approximations obtained from standard finite-difference techniques. Not only are much greater accuracies obtained, but computer times are also greatly reduced. The application of this technique to multiphase flow problems (e.g., single well coning problems) would have considerable practical interest, but such extensions of this technique with full mathematical rigor have not been made as yet. However, the numerical methods presented here are general, and in principle extend to multidimensional, multiphase flow. Moreover, the preliminary results given in this paper are sufficiently encouraging that we feel the effort in attempting these extensions is justified. INTRODUCTION The problem of obtaining accurate pressure distributions and pressure gradients around wells is of considerable importance in the numerical simulation of reservoir performance. The most common approach to solving this problem is to use finite difference techniques (see McCarty and Barfield9 or Peaceman and Rachfordl0). This approach, however, has many disadvantages, the major one being that many grid points are generally necessary for accurately describing the pressure distribution and the pressure gradient around wells. This need for a fine grid results in large computer times and often in prohibitively high costs. Besides investigating the method of finite differences, some authors, such as Welge and weber17 and Roper, Merchant and Duvall,13 have considered a combination of analytical and numerical techniques with some success. These approaches, however, are all nonrigorous and quite often cannot even be applied. In this paper, we present a numerical formulation of high-order accuracy, based on the Galerkin method, for solving this problem. We treat here only the partial differential equation that describes steady-state, single-phase flow. However, the methods presented are general and in principle extend to multidimensional, multiphase flow. Specifically we treat special cases of the problem in two dimensions described by: where G is a rectangle (with sides parallel to the coordinate axis) with boundary ?G, ?/?n denotes the outward normal, and y and B are non-negative constants such that y + B > 0.

Jan 1, 1970

By More-O&apos, R. C. Ferrall, J. W. Wilson

SYNOPSIS The theory of elasticity has been shown to provide a means of determining the stresses and displacements induced by mining in deep level hard rock mines. This theory has been incorporated into an electrical resistance analogue on which the plane of a reef or ore-body can be modelled to enable the rapid determination of stresses and displacements at points in the plane of the reef. This electrical analogue has been used to determine energy release rates caused by scattered mining, which, to some extent, is a measure of the degree of hangingwall fracture. A correlation between predicted energy release rates and actual underground conditions in stopes in the O.F.S. goldfields has been encouraging enough to define parameters on which future stoping layouts can be based. The use of the elastic theory through the analogue has been extended to the assessment of the influence of stoping operations on off-reef excavations. Underground conditions at damaged and undamaged areas have been compared with predicted elastic stresses at the positions under review, resulting in the derivation of design parameters for use in siting off-reef excavations in the prevailing geological conditions in the O.F.S. and Klerksdorp goldfields. The analogue has also been used to assess the vulnerability of certain un mined dykes to bursting. Correlations between stresses induced on dykes by stoping and dyke behaviour underground has enabled critical stress levels to be determined for several persistent dykes occurring in the O.F.S. and Klerksdorp goldfields. A number of long and short term planning projects at mines operating in the Anglo American Corporation and General Mining and Finance Groups are described, where the data derived from the electrical resistance analogue is processed by computer programmes and assessed on the strength of the design factors derived from the correlation of field work and the elastic theory.

Jan 1, 1970

By Fred H. Lippold, Wm. H. Wolf

Methods of fair payment for excavating, supporting, and concrete lining tunnels have been sought by various owners for years. Tunneling techniques have changed with the development of equipment-from the hand-mucking operation to the machine mucker and, most recently, to machine-boring; from tunnel supports using timber sets to steel sets to rock bolts and, most recently, to shotcrete support; and from hand-placing the concrete lining using wooden forms to pumping or pneumatic placing using steel forms. As tunnel construction techniques advanced, so did methods for payment for the work performed. The recent development of tunnel-boring machines, or "moles," is precipitating another change. These changes have led to some difficulty in providing proper payment for the various items of work for different types of tunnels. As a major construction agency engaged in water-resources development in the western states, the U.S. Bureau of Reclamation has long been aware of the need for clarification of payment provisions in tunnel construction. The Bureau has some 150 miles of tunnels completed on its projects and about 50 miles of tunnels under construction. In this construction, the Bureau has benefited by the advance made by contractors in improving the techniques of tunnel excavation. To assure that the Bureau has an up-to-date approach to payment provisions, the Chief Engineer recently established a "standard" method of payment for all types of tunnels. It is believed that this new method of payment will be equitable for all contractors bidding on various types of tunnels using the diversity of methods of excavation now available to them. These payment provisions provide for different quantities for excavated tunnels using the blasting technique or using machine-boring techniques. In this way, the contractors have a choice in excavation methods and an equal opportunity to be low in their bids. We believe this will be an incentive to all contractors to be as progressive as the development of new equipment economically allows.

Jan 1, 1970

By Volkmar Niemitz

Approximately 30 miles east of Chicago on the southern shores of Lake Michigan stands Bethlehem Steel's newest fully integrated steelmaking facility - the billion dollar Burns Harbor plant. The initial phase of "green field" construction that began in 1963 was directed to the creation of high quality finishing facilities. In late 1964 the 160" plate mill came "on stream" followed closely by Sheet and Tin and Hot Strip facilities. Unit train shipments of slabs primarily from the Lackawanna plant located near Buffalo constituted the input materials for the new mills. In 1967 a hot metal facilities program was announced for Burns Harbor that at its completion would make the plant fully integrated. Incorporated within the program were: 1. A new high performance 50" x 96" slabbing mill complete with a battery of soaking pits. 2. A two vessel Basic Oxygen Furnace Shop. 3. (1) battery of 6 meter high Coke Ovens with attendant coal handling facilities. 4. A 3800 feet long vessel loading & unloading dock. 5. The first conveyor belt fed Blast Furnace in the United States. 6. An extensive materials handling system for receiving, stocking and reclaiming from storage the raw materials for the Blast Furnace and Coke Ovens operation. The intent of this paper is to provide a detailed description of the functions and components of the materials handling system noted above.

Jan 1, 1970

By J. J. Frawley, W. J. Childs

Experiments were carried out to induce grain refinement during solidification by applying vibrational energy (freq 20 kc) to small specimens of bismuth, tin, and bismuth-tin alloys. The results show that if the intensity of the applied sound -field is not great enough to fragment the growing dendrites of a pure metal, no grain refinement is observed and the pain size of the dynamically nucleated specimens is the same as the grain size of a specimen statically supercooled the same amount. Bismuth specimens did not show any grain refinement; whereas, the tin specimens did show grain refinement. This phenomenon is the result of the difference in growth habit between the bismuth and tin dendrites. The bismuth-tin alloys showed grain refinement and, in addition, the segregation pattern was changed. THE solidification process is a change in phase requiring the nucleation of the solid phase from the liquid and the growth of this solid phase at the expense of the liquid phase. Since many physical properties and also the integrity of a casting are dependent on the solidification process, understanding and controlling this process are very important.' A good example in the controlling of a cast structure using heterogeneous nucleation theory is the reduction of grain size in aluminum castings by nucleation catalysis.2 This mechanism of nucleation catalysis has been explained by Turnbull.3 Another technique for grain refinement, which has received much attention but the mechanism has not been fully understood, is to vibrate the solidifying melt. Vibrations can be applied to the melt either by vibrating the mold directly or by introducing a vibrating rod into the melt.4-13 Three mechanisms have been proposed to explain this phenomenon: 1) The mechanical fragmentation of the original dendrites that grew into the melt. These crystals or fragmented dendrites act as new growth sites. 2) The nucleation of new grains in the liquid by the generation of very high pressure pulses caused by cavitation in the liquid. 3) The remelting of the dendrite arms during the solidification process. This mechanism is operative only in alloy systems and would be enhanced by stirring or mechanical vibration. The purpose of this investigation was to determine the mechanism that will increase the number of grains when mechanical energy is introduced into a solidifying melt. APPARATUS The unit used to generate the ultrasonic vibrations was manufactured by the Redford Co., and is similar to the one used in ultrasonic soldering. Fig. 1 is a sketch of the major components used for generating ultrasonic vibrations. The crystal transducer assembly consisted of four lead zirconate ti-tanate piezoelectric crystals in an aluminum holder. An acoustical horn, which was fabricated from stainless steel, was attached to the holder by a set screw. The resonant frequency of this unit was 20,000 cycles per sec. A Pyrex crucible, 4 in. in diam and 4 in. high, was contained in a hole in the top of the horn. The piezoelectric crystals changed volume when excited by an electric signal, thereby generating a sound signal which passed through the horn. The crucible was coupled to the horn by a liquid silicone oil. The purpose of the couplant was to transmit the soundwaves from the horn to the crucible. Without the couplant, much of the sound energy would be lost. The energy transmitted was sufficient at the resonant frequency used, so that acoustical cavitation always occurred in the molten metal. The presence of acoustical cavitation was detected by the characteristic hissing sound emitted from the liquid. EXPERIMENTAL PROCEDURE The influence of ultrasonic vibration on the grain refinement of bismuth, tin, and bismuth-tin alloys was studied. These metals were chosen because of their low melting temperature and the relative ease with which they can be thermally supercooled. The following procedure was used for obtaining large amounts of supercooling. Pure bismuth (99.999+), which was received in bar form, was mechanically broken into pieces small enough to be accommodated in a 50 ml beaker. About 200 to 300 g of bismuth and a few grams of SnCl2 as a flux were placed in the 50 ml beaker and melted by induction heating. The melt was held for 20 min at

Jan 1, 1970

By H. D. B. Wilson

THIS PAPER has resulted from a preliminary draft of a background paper prepared anonymously for the Science Council's Special Study of the Solid-Earth Sciences in Canada. The draft was circulated to eighty-four Canadian geologists; forty-eight of these responded with criticisms of the draft. All critical re-marks were considered carefully and most have been incorporated in the final paper in an attempt to balance the author's bias, although this bias undoubtedly still appears. Indications of support for a particular statement or section were also helpful, because many of these contradicted criticisms and enabled the author to judge the consensus. Thus, all criticism could not be incorporated because the referees did not agree. It is interesting that some remarks were con-sidered overstatements by some and too bland by others. The most perplexing critical comment was one which suggested a new author was needed, and went on to name the existing author as the most likely candidate.

Jan 1, 1970

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

The effects of detonation of downlines and downline-booster systems on lodse-poured charges of 94% porous prilled ammonium nitrate/6% fuel oil (AN/FO) were determined. Detonation stability was indicated by the initiation-failure pattern of detonating fuse witness lines located at intervals along the charge. Steel tubing was used as the confining medium. Charge diameters (d) varied between 2-21/32 and 8.1/8 in. and specific charge weights (w) of downlines between 4.0 and 93.2gr/ft. The axes of charge and downline were colinear. The minimum value of w required to cause initiation of AN/FO increased with d. When initiated by a downline only, the charge'underwentlowòorder detonation. When downline-booster systems are used, the detonation wave in the downline cuts all equatorial planes in the charge before the detonation wave in the surrounding AN/FO. If the downline itself does not cause initiation, therefore, the explosive ahead of the main detonation wave is crushed, and hence desensitised, by the radially-expanding compression wave and gases generated by the downline. In a given equatorial plane, the fraction gftharge undergoing detonation decreases with an increase in the booster-plane distance. The longitudinal limit of nation increases significantly with d, but surprisingly little with a decrease in w. In the presence of a downline, the blasting performance of AN/FO charged _

Jan 1, 1970

By Richard F. Zaffarano

The Bureau of Mines compiled information for the nonspecialist about natural gas liquids recovery from hydrocarbon streams in natural gas processing plants. Attention is directed to the impact of the technology of processing and the quality of gas processed in view of the increased availability of natural gas for processing. Significant changes in product and market trends within the natural gas processing industry are highlighted. Fixed capital-plant costs for grassroots, refrigerated-oil absorption and conventional adsorption schemes, adapted from published studies, are presented giving ranges of cost estimates for medium-sized plants. Marketed products of the natural gas processing industry are briefly discussed in relation to automotive air pollution problems and approaches to their control.

Jan 1, 1970

Jan 1, 1970

By R. C. Hirschfeld, H. H. Einstein, R. W. Bruhn, R. A. Nelson

The objective of the model studies described in this paper is to determine the effect of planar discontinuities on the strength and deformability of a rock mass. A model material was used because it satisfied concurrently three requirements that available natural-rock samples did not: (1) low strength, which was desirable for minimizing the loads that had to be applied in the laboratory; (2) ease of producing test specimens with geometrically regular joint patterns; and (3) uniformity of the test specimens. The model tests were performed on specimens made from a single modeling material and tested under triaxial stress conditions with [u,=u,]. Results are presented in this paper for tests on specimens that had (1) a single joint set inclined at several angles to the major principal direction, including 0º and 90°, and (2) two joint sets that were mutually perpendicular, one set perpendicular to and one set parallel to the major principal direction. Several different joint spacings were used in each series. Future tests will include a series with two sets of joints that make oblique angles with each other and with the major principal direction. The results of model tests and tests on cores of jointed rock by several investigators (e.g., Müller and Pacher,l Moore,2 Krsmanovic and Milic,3 Hayashi,4 Rosenblad,5 Jaeger,6 and Lane and Heck 7, have contributed significantly to the design of these experiments, which are believed to be the first in which a comprehensive study has been made of the combined effects under triaxial loading of joint spacing and joint orientation (Fig. 1).

Jan 1, 1970

By Immo H. Redeker

This is a final progress report on a cooperative project conducted by three private feldspar companies,** North Carolina State University, and the federal Bureau of Mines. The object of the project was to reduce the feldspar tailings disposal problems at the flotation plants in the Spruce Pine area of North Carolina. The initial phase of the project revealed that high tonnages of saleable feldspar and quartz were lost in the tailings and the three feldspar companies are now concentrating their efforts on feldspar recovery, either by reclamation from the tailings as suggested by the Asheville Minerals Research Laboratory or by improvements in metallurgy in the existing plants.

Jan 1, 1970

By Joseph L. Condon

Fifteen shots of three explosives with charge weights of 0.52, 1.1, 3.1, and 5.1 kilograms were fired in a pond to study the seismic effects of detonating explosives in water. Shock pressures and bubble periods were measured with pressure transducers in the water. Vibrations were measured on land in three orthogonal directions with particle velocity gages. Statistical tests indicated that a charge weight exponent of 0.43 best scaled the data. While shock pressures and bubble periods showed considerable differences in explosive performances, the amplitudes of ground vibrations showed less difference, and one prediction equation was therefore derived to estimate vibration amplitudes from all the explosives.

Jan 1, 1970

By E. J. Krokroskia

Fletcher Mill is located in the southern part of the New Lead Belt in Southeastern Missouri, in the northwestern part of Reynolds County. Shaft sinking began in July, 1964. The mill went on stream in February, 1967, and reached the designed rate of 5,000 tons per day in July, 1968. The ore occurs approximately 1,000 feet below the surface as disseminated deposits of galena, sphalerite and chalcopyrite. There is no oxidation within the ore body and dissemination is not fine enough to present liberation problems with a normal grind. Mining is by the room and pillar method with rubber-tired diesel- propelled drilling and loading equipment. The ore is dumped through a 27-inch square grizzly into a 5,000-ton pocket. The underground primary crusher is automatically fed by a vibrating feeder and discharges directly into skip measuring bins. Hoisting is automatic, in balance, with 8. 5-ton skips dumping into a 1,000-ton mill bin. MILL The concentrator is a 5, 000 tons-per-day single section plant equipped to produce lead, zinc and copper concentrates. Contained under 35, 347 square feet of roof, without fine ore storage or remote crushing, and with sufficient automation to be operated by one man, the plant is compact, unique, and efficient in operation. The design

Jan 1, 1970

By Milton E. Wadsworth

The reduction of a metal in an aqueous solution may be defined in terms of its source of electrons. In electrolytic reduction electrons flow as a result of applied voltages. In other systems electron sources are reducing gases or metals of lower electron affinity. In the latter two cases it is increasingly evident that reduction is electro-chemical in nature in that electrons flow through one or more conducting phases even though the discharge reactions may not be rate controlling. Electrode processes impmtant in reduction and metal deposition are reviewed and extended to contact reduction by precipitation (cementation) on mme electropositive metals. Contact reduc- tion Processes are ancient in origin and represent techniques which have had successful application for hundreds of years. In spite of this, little has been understood in terms of the dynamic properties of such systems or of important side reactions. In recent years an increasing amount of laboratory work has been carried out on contact reduction and an attempt is made here to summarize the important findings. Undoubtedly the interest aroused recently may be attributed to improved reactor design which has demonstrated on a commercial basis accelerated metal recovery by taking advantage of important kinetic and chemical parameters. of gold cyanide (Au(CN)-), respectively. The most common method for the reduction of ions in solution is by electrolysis. The impure metal is made the anode and the ions are reduced at the cathode. Leach liquors containing reducible ions may similarly be reduced electrolytically using an inert anode. The latter process is referred to as electrowinning. In recent years hydrogen has been used successfully as a gaseous re-Metallurgical Society of the American Institute of Mining, Metallurgical and Petroleum Engineers (AIME). He was also a member of the Executive Board of the Metallurgical Society (AIME). In 1957 Dr. WADSWORTH was given the AlME Best Paper Award as coauthor of a paper on the roasting of sphalerite. On July 1, 1968 Dr. WADS-WORTH started an 24 month assignment in the Philippine Islands to assist in the development of graduate metallurgical engineering at the University of the Philippines. In addition to graduate teaching and curriculum development he will establish research programs to develop extraction processes for metals production in the islands. The project is supported by the Ford Foundation through Educational Projects, Incorporated.

Jan 1, 1970

By S. R. Balajee, I. Iwasaki

The adsorption mechanism of corn starch and its derivatives at mineral-solution interfaces was investigated by the adsorption of cationic starch, unmodified corn starch, British Gum 9084, and anionic starch on quartz and hematite. The adsorption of these starches, which decreases in the order mentioned, is dependent on the balance between the magnitude of the electrostatic interaction and the magnitude of the hydrogen bonding. There exists a critical starch concentration for both optimum flotation and flocculation conditions of iron ores, which corresponds to a point where the starch adsorption reaches a saturation coverage. Flocculation occurs due to the adsorption of starch via electrostatic and hydrogen-bonding forces and by interparticle bridging as a result of the conformation of starch molecules at the interface. The depressant property of starches and starch derivatives in flotation' and their flocculation char: acteristics in clarification and filtration2.3 have long been recognized on a wide variety of ores. The effectiveness of a starch as a depressant for iron minerals has been the subject of much investigation in recent years both in the amine flotation of siliceous gangue and in the anionic flotation of activated silica from iron ores. It has been reported that the depressant activity of starches and dextrins in the cationic flotation of quartz from hematite increases with molecular weight, branching, and number of hydroxyl groups, 1 and that the selectivity is affected by changing the configuration of starch molecules and the composition of its polar groups.4 ,5 The manner in which starches are solubilized was shown to exert a significant influence as a depressant in the anionic silica flotation, and a series of articles covering the practical aspects of flotation and flocculation have already been reported.618 Chemical modification of the starch structure, the pulp pH, the calcium ion, and the residual starch concentration were identified as some of the more important variables affecting the flotation behavior. In the flocculation of iron ores, it was noted that most starches flocculated suspensions of hematite in water but did not flocculate similar suspensions of quartz,9 and that an excessive use of starch restabilized the suspensions due presumably to protective action. 6 An admirable application of such an observation to practice may be cited in the selective flocculation and desliming in the anionic silica flotation of iron ores, which resulted in superior metallurgy and lower reagent cost. 10 From detailed adsorption measurements, Schulz'and Cooke4 established that the adsorption of starches and their derivatives depended on the types of minerals and of starches, pH, and electrolytes present. Their adsorption data and the foregoing flotation and flocculation observations suggested that an electrical interaction between starches and charged mineral surfaces might be playing a role in their adsorption process. Adsorption of organic polymers, particularly of synthetic origin, at solid-liquid interfaces has been extensively studied in recent years,' and it is realized that their adsorption mechanism is considerably more complex than that of simple ions or molecules. A polymer molecule possesses a number of functional groups, and the adsorption at a point may restrict the adsorbability of adjacent groups. The mechanism may be further complicated by the conformation of the polymer molecules which may exist as coiled spheres, helices, or extended chains as a result of intramolecular interactions among functional groups as well as intermolecular interactions with solvent molecules. The object of the present investigation was to examine the effect of the chemical modification on the adsorption characteristics of starches and starch products on quartz and hematite at several pH values, so that by correlating this information with flocculation and flotation results, adsorption mechanism of starches on mineral-solution interface may be elucidated. EXPERIMENTAL MATERIALS Quartz: St. Peter sand was screened at 35 mesh and the undersize was scrubbed and deslimed at a Fagergren cell. The deslimed sand was cleaned with 0.1 N hot hydrochloric acid and washed repeatedly with distilled water, For anuscript, measurementsl the -200-mesh fraction of the sand was ground dry in a porcelain mill for 3 hr. The specific surface of the finely ground quartz was

Jan 1, 1970

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By P. R. Swann, R. M. Fisher, W. R. Duff

Observations by transmission electron microscoPy of the microstructures in quenched Fe-A1 alloys provide the basis for revision of the Fe-A1 phase diagram. The diagram is characterized by first-order transitions between the disordered ferromagnetic a! solid solution and the two ordered phases FeAl and Fe3Al. However, second-order transitions showing corre-luted fluctuations in the degree of order near the critical temperature occur between the paramagnetic a! and FeAl and the FeAl and FeAl phases. ELUCIDATION of the true nature of the Fe-A1 equilibrium diagram has proven to be an extremely challenging problem as evidenced by the fact that six quite different versions of the iron-rich portions have been published since 1958.&apos;-6 The most recent diagram shown in Fig. 1 was proposed by Rimlinger6 based on X-ray diffraction analysis and dilatometry. He shows the single-phase fields of the ordered phases of the types FeAl(L20) and Fe3A1(D03) and the disordered bcc Fe-A1 solid solution, a, separated from one another in every case by large two-phase regions. Thus, he implies that in Fe-A1 alloys ordering always occurs via a classical phase transition. In contrast to this view, theoretical studies3&apos;" have concluded that the transitions a — FeAl and FeAl — Fe3A1 should be second- or higher-order in character. A further revision of the Fe-A1 diagram of state is presented in Fig. 2 based on our previous8,9 and current observations by transmission electron microscopy of the microstructures found in quenched specimens. The average quenching rate was 50,000°C per sec and although this was sufficiently rapid to prevent Fe3A1-type ordering below -550°C it was not sufficient to suppress ordering of the type FeAl in the temperature range -650" to 800°C. However, ordering during the quench is easily recognized since the FeAl phase formed during holding at temperature rapidly develops large antiphase domains whereas FeAl formed during quenching has a very fine domain size, -50Å diam. Each symbol in Fig. 2 indicates the result of a micro-structural examination of specimens heat-treated (-1 hr) until equilibrium was established. The results will be discussed in the order of the points, A - Dl marked on both diagrams with reference to the phase fields, critical temperature, and "transition" ranges, respectively. The dark-field micrograph corresponding to point A is shown in Fig. 3 and was obtained using a 111 reflection of the Fe3A1 structure which reveals both a&apos;/4<111> and a&apos;/2<100> antiphase domain boundaries.10 The structure observed in this specimen is typical of single-phase Fe3A1 and shows no evidence for FeAl or any other additional phase. The dark-field micrograph shown in Fig. 4 corresponds to point B on the two diagrams. It was taken with a 100 FeAl reflection which reveals a/2(111) domains and exhibits the typical structure of single-

Jan 1, 1970