Search Documents

By Charles Y. Clayton, Henry S. Burnholz, Francis B. Foley

This work was first undertaken for the U. S. Bureau of Mines, in 1919-20, by C. E. Julihn, superintendent of the station at Minneapolis. Learning of the interest, in this subject, of B. F. Tillson, of the New Jersey Zinc Co., Mr. Julihn and Mr. Foley went to Franklin, N. J., and discussed the matter with him. A conference in Chicago, in November, 1920, was attended by Dr. F. G. Cottrell, who was then Director of the Bureau of Mines, and representatives of the Bureau of Mines and of the hlissouri School of Mines and Metallurgy; at this time a cooperative plan of work was agreed upon by the Bureau of Mines and the Missouri School of Mines. In February, 1921, Mr. 'Tillson arranged a conference on this subject at the time of the annual meeting of the American Institute of Mining and Metallurgical Engineers, at which several technical papers were presented. In a paper, the Breakage and Heat Treatment of Hock Drill Stcels, he suggested a program that might be carried out in connection with the investigation of the problem. At this conference Mr. Manning, former Director of the Bureau of Mines, suggested the formation of an advisory committee to the Bureaus of Mines and of Standards for prosecution of this investigation. On Feb. 20, 1922, a secoud conference in New York, at the time of the annual meeting of the American Institute of mlining and Metallurgical Engineers, was attended by representatives of various technical societies. At this meeting, the report of Nov. 20, 1921, of the Chiefs of Divisions of Metallurgy of the Bureaus of Mines and of Standards, was discussed and it was agreed: 1. That the survey recommended by the two bureaus should be undertaken, which survey would have for its object the ascertaining of the present status of the practice of the heat treatment of drill steels, the extent to which the breakage occurs, etc.; and 2. That a report should be presented, of the findings of those who made the survey, to the Advisory Board to the Bureaus of Mines and of Standards. The Bureau of Standards assigned $4000 to the prosecution 01 a three-months' survey, which was carried out in April, May, and June, 1922, of about sixty mines

Jan 1, 1923

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship' to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,' using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager's extenbion of Fick's first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964

By F. G. Miller

Earlier studies of the mechanism of flotation showed that coal flotation products are contaminated by composite coal and mineral particles. The mineral matter of these particles has the dual effect of increasing the specific gravity and decreasing the coal surface of the particle available for bubble attachment. The present study showed that these particles are more loosely held in the froth column than the high grade coal particles, especially in the coarser sizes. Consequently, it is possible in the laboratory to produce a secondary concentration of the product by sprinkling the froth product with water to wash these loosely held particles from the froth during formation and recovery. To improve coal flotation, Bethlehem Steel Corp.'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 studies1 of each physical factor have produced immediately usable results in commercial coal flotation and are providing the basis 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 14 mesh 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. These principles and findings, together with work by Professor V. I. Klassen,' led to the froth sprinkling investigation reported in this paper. Working with Russian coals, Klassen had shown that froth sprinkling washes loosely held refuse particles from the froth and compensates for the water lost in the upper froth layers and increases its stability. As a result, the coal particles are retained in the froth and the loss of coarse coal from the froth is prevented. Decreases in ash of 0.1% to 1.5% were reported by Klassen. Working with a 28 mesh x 0 American coal, the author of the present paper found that single-stage flotation coupled with froth sprinkling produced a product comparable to that obtained by the more expensive method of roughing and cleaning.3 The investigation reported in the present paper expanded study of the effect of froth sprinkling to include each of the standard size fractions of a bituminous coal. The main findings are as follows: (1) For those size fractions between 48 mesh and 150 mesh, froth sprinkling produces a marked reduction in both sulfur and ash. In the case of those sizes coarser than 48 mesh, while this reduction is not as significant, the additional benefit of shorter retention time is still a plus for froth sprinkling. Furthermore, when froth sprinkling is coupled with normal fast flotation, the product purity approaches that obtained by starvation reagent feeding, i.e., gradual feeding of flotation reagent to float the recoverable coal from the pulp slowly in several increments. The specific results for these two size groups are: (a) 14 x 48 Mesh. By using froth sprinkling with fast flotation, product sulfur can be reduced to a level

Jan 1, 1970

By J. M. Camp

In conforniity with the design of the oficials of the United States Steel Corporation for the standardization of the methods employed in the sampling and analysis of all materials encountered in their various lines of manufacture, the Chemists' Committee presents this compilatioti of standard methods for the sampling and subsequent analysis of molten pig-iron. In selecting the methods, the Committee employed the same line of procedure as in former cases, viz., the careful consideration of all the methods employed in each laboratory of the Corporation, evolving therefrom the several methods herein described, the immediate adoption of which is desired. The services of Messrs. W. B. N. Hawk, William Brady, and C. H. Rich, a sub-committee appointed for the preparation of the present paper, are gratefully acknowledged. II. Introduction. A quite obvious cause of nonconformity of results of comparative analyses in the various laboratories of the Corporation has been an apparent lack of uniformity of method in the sampling and analysis of molten iron. This condition is particularly apparent with regard to the determination of the sulphur, numerous discrepancies in which would appear t.o indicate the absence of, and the necessity for, some uniform method of procedure. The estimation of the

Jan 1, 1913

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

An analytical study is made of thermal stress distribution in a thin circular disc subjected to a peripheral thermal shock at various rates of heat transfer. The problem is of importance in predicting the thermal shock response of a rock body of finite size. The theoretical analysis is based on radial heat flow by conduction in the disc and heat exchange by convection between the disc and the surroundings. The case of constant properties and plane stress is treated. Solutions of the stress distribution are presented for both cooling and heating shocks and an average stress theory is formulated. Preliminary experimental verification was obtained from the results of shock tests on thin rock discs insulated on both flat end faces so that heat exchange took place through the exposed peripheral surface. Physical properties vital to the analysis are Young's modulus, tensile strength, coefficient of linear thermal expansion, thermal diffusivity and thermal conductivity. Plots of these properties are presented. Historically, thermal energy has been used for primary rock removal throughout the ages. Although it is not widely known, the fire-setting method of thermal rock fragmentation was still in use 100 years ago in systematic underground mining operations in Scandinavia.' There, the availability of cheap labor and abundant wood fuel made the method competitive with the early blasting powders. By 1880, as high explosives replaced powder, use of the method declined and it was finally abandoned about 1885. Only 40 years ago, some experimental fire-setting methods were used for rock removal underground at Pribram and Zinnwald in Central Europe.2 Compressed air-oil burners replaced the earlier wood fuels. About 15 years ago, gaseous oxygen-oil burners were introduced in the United States and gained acceptance for difficult blasthole drilling and some quarry opera- tions. At present, there is renewed interest in the compressed air-oil burner designs. The literature included information on thermal secondary processes for rock weakening or particle liberation3,4,5,6,7,8 on thermal spallation of rock 9,10,11,12,13 and on the thermal fracture of materials other than rock. The 1955 Symposium on Thermal Fracture14 and the later work of Hassel-man, cover recent developments in thermal shock investigations on brittle ceramics. Although the number of published analytical and experimental investigations conducted on ceramic and refractory materials is large, the literature reveals that there is a lack of information on both the theoretical and actual response of rock to thermal shock. Many of the thermal shock studies on ceramic and refractory bodies are based on the case of heat transfer at the solid's surface by convection in either liquid or air. A similar heat transfer situation was adopted for a theoretical analysis of the thermal stresses in a thin circular disc subjected to a peripheral thermal shock. Experimental thermal shock tests were then conducted on rock specimens to check the analytical results. Specially insulated quartzite, basalt and taconite discs were shocked in either liquid or still air bath at various rates of heat transfer. The work was done in order to resolve the question as to whether theoretically determined tensile stresses are actually realized in a finite rock body undergoing thermal shock. Specifically, if theory predicts that the tensile strength of a rock should be exceeded in a particular type of controlled thermal shock, will fracture occur? This information is needed by Bureau researchers working on thermal and electrical rock fragmentation methods. The object of this paper is to present the main features of the theory and procedure being used in the authors' approach to quantitative prediction of rock response to a thermal shock. THEORETICAL ANALYSIS In the analysis to follow, simple geometry of a thin circular disc is considered. The disc is assumed to be isotropic, homogeneous and perfectly elastic, and to have constant thermal and mechanical properties. The effect of radiation is neglected so that heat is transferred by conduction inside the disc and by convection with its surrounding. In addition, the end

Jan 1, 1967

By J. E. Tiffany, S. S. Lubelsky

For blasting in coal mines the U. S. Bureau of Mines recommends that permissible explosives be used exclusively, that these shall be fired electrically, and that where feasible the working place shall be cut or sheared. These recommendations are made to promote safety and prevent mine explosions. Although permissible explosives are not flameless, their lower flame temperature and shorter duration of flanie make their use safer than that of nonpermissible explosives. Mixtures of air with both methane and bituminous coal dust, which are liable to occur in coal mines, may be ignited by coming in contact with any type of flame or spark of sufficient temperature and duration or by the firing of a blast. In a working place where a blast is to be fired, in addition to the use of permissible explosives, adequate ventilation for the dilution and removal of accumulations or outbursts of flammable gas should be provided. Bituminous coal mines should be rock-dusted as a means of rendering the coal dust harmless The efficient use of permissible explosives depends upon the proper preparation of the working place, standardized drilling, the strength characteristics of the explosive, and the use of a proper weight of charge. Experienced shotfirers should load, tamp and fire all holes. The major part of the information and data here presented is based on the results of efficiency tests made in large producing mines of Pennsylvania and Illinois. Bureau of Mines Report of Investigations, Serial No. 2697, describes how a standard method of blasting was worked out and put into operation in a mine in southern Illinois.' This paper contains a description of the methods worked out subsequently in another mine in that district. Descriptions of tests in two Pennsylvania mines are given in Bulletins 11 and 19 of the Carnegie Institute of Technology.2 These tests

Jan 1, 1928

NEW MEMBERS The following list comprises the names of those persons who became members during the period of Apr. 10, 1918, to May 10, 1918. BALLARD, JOHN I Supt., Cable Mining Corpn., Cable, Mont. BURKMAN, JOHN M. F., Constr. Engr., U. S. Smelt. Refin. & Min. Co., Care -University Club, Mexico City, D. F. CALLEN, ALFRED COPELAND, Head, Mining Engineering Dept., West Virginia University Morgantown, W. Va. CHADWICK, LAWRENCE, Chem., Mt. Elliott Copper Co., Ltd., Selwyn, via Townsville, North Queensland, Australia. CODY, FRANK W., Skimmer, Reverberatory Furnace, Arizona Copper Co., Clifton, Ariz. COOLBAUGH, MELVILLE F., Prof. of Chem., Colorado School of Mines, Golden, Colo. DODGE, ALLAN WAYNE The Dodge Agency, 104 East Iron Ave., Salina, bans. DONNELLY, LEONARD G., Pet. Geol., Sinclair Oil & Gas Co., Sinclair Bldg., Tulsa, Okla.

Jan 6, 1918

By C. C. Harris

The characteristics of some common size distribution equations are critically discussed. A generalized form of several well-known size distribution equations is obtained from a differential equation describing statistical distributions. The equation contains three parameters and can describe the major features of size distributions in the fine and the coarse size regions. A graphical method for its implementation is provided. The application of this and other equations to sets of data are compared both for the quality of fit and from a comminution kinetics viewpoint. If a narrow size range of a brittle material is broken sufficiently to obliterate the feed sizes, but not so severely that excessive secondary breakage occurs, a plot of cumulative fraction by weight undersize (Y) vs. sieve size (X) on a log log grid (sometimes called the Gates-Gaudin-Schuhmann plot)1-3 gives a straight line of slope ~ 1 over much of its range. On closer inspection, deviations in the extreme coarse range covering perhaps 10 to 30% of the total sample may be apparent (frequently, a change in slope from ~ 1 to a value different from unity) together with over-all slight irregular departures from a smooth line. One model of breakage postulates that the same fracture pattern persists throughout all size ranges.4 The fracture pattern is characterized by the slope of the line on a log log grid. Accordingly, a distribution of sizes broken in the manner specified earlier is expected to produce a size distribution having the same slope as that of a broken narrow size range. Additionally, the slight irregularities mentioned above should even out in the summation process, giving a smooth straight line of slope ~1 on a log log plot. This idealized state of affairs does not, however, describe the distribution of a multi-event process such as that for a tumbling mill product. On the average, these curves (plotted again log log) tend to have a slope in the fine region different from and usually less than unity,5 while the coarse size region curves with increasing slope for cases of mild reduction, and with decreasing slope when moderate or severe size reduction has occurred. In addition, there are usually slight irregular deviations from a smooth curve. Most curves display two distinct regions — fine and coarse — and a few curves show one or more intermediate regions. Feed size studies6,7 show an effect which theory is required to explain. For the same material, mill loading and other operating conditions, and the same time of grinding, plotting the dimensionless ratios Y vs. X/(feed size) does not reduce the size distribution data to the same curve. Y vs. X does not correlate the coarse region, but it can provide a crude correlation of the fine region which improves as size diminishes and as grinding time increases. The size distribution in the coarse region is somewhat more dependent on the feed size than is the distribution in the fine region wherein the degree of dependence diminishes as time proceeds; the distribution of sizes in the fine region are determined largely by the nature of the material and the comminution conditions. A comprehensive model of comminution must recognize that several different patterns or modes of breakage can occur in a mill; 5,8,9 that there can be some selection in that some size ranges are broken more than others; and that, while some particles may be the product of a single fracture event, or may even remain unbroken, others result from multiple rebreak-age. Thus, breakage in a tumbling mill is more complex than the Schuhmann4 model admits in that several different types of comminution micro-events* occur rather than just one type, and these events, though different in size scale, are of the same overall pattern as that which is visualized by the model. The concept of an average comminution micro-event has, therefore, a mathematical rather than a physical connotation, at least for tumbling milling. Equations with which to describe particle size distributions have been sought for over half a century.10-13 No equation presently in general use was first derived from an analysis of the statistical mechanics of breakage; whatever theoretical basis the existing

Jan 1, 1969

By Albert J. Phillips

As EARLY AS 1824, Haidinger1 described crystals of native copper that were, according to Dana,2 "probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

Jan 1, 1928

By M. G. Magnuson, H. O. Hofman

When dry chlorine gas is made to act in the cold upon fiuely-divided gold,' it converts the latter with evolution of heat into auro-auric chloride, Au4 Cl4, a hard, dark-red, hygroscopic salt. Moisture splits this salt into aurous and auric chloride, Au²C14 = AuCl + AuCl³; treatment with water converts it into auric chloride and gold, 3 Au²CI4 = 4 AuC1³ + Au². Aurous chloride, when stirred with water, undergoes a similar decomposition, 3 AuCl = AuCI, + Au,. These decompositions of auro-auric chloride and of aurons chloride furnish the explanation for the practice of moistening an ore before it is treated by the Plattner chlorination-process; practical experience having shown that gaseous chlorine gave an unsatisfactory extraction with dry ore. According to Rose12 fine gold is acted upon more slowly by chlorine than gold containing some base metal, e.g., copper. He also says that small quantities of silver increase the rate of solution, but adds that the coating of silver chloride formed, checks, and finally stops, further action, if the percentage of Silver be increased beyond a certain undetermined amount. Bromine3 acts upon finely-divided gold in a manuer similar to chlorine; the auro-auric bromide, Au²,Br4,, however, is not hygroscopic. Upon treatment with water it is decomposed as is the corresponding chlorine salt. It is generally believed that bromine does not act as energetically upon gold as does chlorine. This seems to be borne out by the results in the leach- +1MASSACHUSETTS INSTITUTE OF TECHNOLOGY, BOSTON, MASS.

Jan 1, 1905

By C. L. Berrien

MANY fires have occurred in the mines of Butte in recent years, and while all have been of a serious nature, simply because they were mine fires, six of them have been especially dangerous in respect to loss of life and property, and the expense of extinguishing or controlling them. It is not my intention to discuss the relative merits of methods used in fighting these different fires because the conditions under which they occurred varied in each case, and it was not always advisable to expend the large sum of money necessary to actually extinguish them if they could he bulk-headed off from the rest of the mine. It is needless to say that everything possible has been done to check all fires at the beginning, but without success in some cases; and it has then become necessary to bulkhead all connections to them, in which state several now exist. The mine fires of Butte, or fires in any mine, may be divided into two classes, namely: Those occurring in accessible workings, and those occurring in inaccessible workings; because these two conditions govern to the greatest extent the methods of fighting fires. Accessibility and in-accessibility in the case of mine fires concern not only new open workings and old closed workings, respectively, but also the condition of the ventilation in and about those places. When a fire is accessible at the start it should not be difficult to confine it to a small area and extinguish it in a relatively short time, but when it is impossible to actually reach a fire in old filled, abandoned workings, or there is no opening by which the gases may be conducted away from the fire zone, then the time consumed in changing those conditions permits the fire to increase to such an extent that it is a long, hard fight to overcome it.

Jan 6, 1915

By G. R. Purdy, J. A. Malcolm

The isothermal dendritic precipitation of y in p CuZnSn is compared with the isothermal formation of Widmanstatten a plates in p CuZn. Although both precipitates are evidently bounded by semicoherent interfaces, the dendritic shape of y evolves through smooth "sinuoidal" shape perturbations, while a-p interfaces tend to be strictly planar, or rnicroscopically faceted. An estimate of the average inter-facial free energy of cube-oriented y in p through the Mullins-Sekerka analysis indicates that it is low (of the order of 50 ergs per sq cm). Interface mication is apparently controlled by volunle dij'usion, and the observed anisotropy in growth probably results from anisotropy of inter facial free energy. Studies of the grain boundary precipitation of y in p indicate that the precipitate can grow in both $ grains, but becomes unstable with respect to the grain with which it shares a mobile semicoherent interface. Facets observed at the tips of Kurdjumov-Sacks-oriented Wid-manstatten a plates correspond to variants of an irrational hahit, near (231)0. Comparison with Hu and Smith's determination of relative interfacial free energies of a-(3 boundaries suggests that this system possesses an extremely deep o cup, which results in an ej'ective low-o zone. The possible effects of such a cup on the stability of a-p interfaces are discussed, a needles, grown during rapid continuous cooling, possess microscopically smooth interfaces, and are characterized by a high degree of' damage in the region of the boundaries. These boundaries, induced to move on tempering at 200"C, become faceted as equilibrium is approached, which seems to indicate that boundary structure and mobility in this system are dependent on the local degvee of departure from equilibrium MULLINS and sekerkal have elucidated the phase boundary stabilizing effect of surface tension. a factor not taken into account in previous treatments of morphological development. Their analysis applies to the isothermal growth of a pure spherical precipitate (planar in the limit of infinite radius) in a slightly supersaturated solution, under conditions of inter-facial local equilibrium and isotropy of interfacial free energy. More recently, several other factors which might tend to stabilize planar interfaces have received attention. These are: i) interface diffusion;4"8 and ii) slow interfacial reaction. cahn7 included a slight anisotropy in interfacial free energy, and showed that it has no stabilizing effect, but forces shape perturbations to reflect the anisotropy. shewmon4 noted that dendritic morphologies are rarely observed in solid-solid systems, and, in particular, postulated that slow interfacial reaction occurs at all boundaries between proeutectoid ferrite and austenite, except those which propagate parallel to {11 l)y planes (for Kurdjumov-Sachs [K-S] related phases). Previously, Aaronson~ had proposed interfacial reaction at the broad faces of Widmanstatten plates, and expected that the lateral motion of high-mobility incoherent ledge edges would produce planar precipitates bounded by law-mobility semi-coherent interfaces. The problem of interfacial reaction during the dif-fusional formation of precipitates has often been ignored, although it is apparent that a small component of chemical reaction must exist at any moving interface." Further, all solutions of the diffusion equations for boundary conditions corresponding to isothermal growth predict infinite growth rate at time zero, so that elements of interfacial reaction would be most easily detected at early times. However, reported deviations from diffusion control are comparatively rare," and the local-equilibrium diffusion-control model appears adequate for the description of many isothermal growth systems.'2"9 Cahn14 has treated the problem of migration of an interface which is able to reach positional energy minima, and concluded that such an interface, if subjected to a high local ther-modynamic "driving force", may migrate normal to itself without the benefit of ledges. As local equi-

Jan 1, 1968

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,' the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O'Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie' has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970

By R. T. Hukki, A. M. Gaudin

Previous work on the principles of comminution has shown: (I) that the surface produced is proportional to work input (Rittinger law,1a-3); (2) that there is regularity to the weight distribution of the fragments according to size.4-10 In this paper it is brought out that the surface on the fragments is distributed in definite and simple relation to size. The experimental work has involved: I. Construction of an apparatus capable of measuring the surface of mineral fragments independently of the chemical composition of the fragments and independently of the site of the surface; 2. Refining the methods available for measurement of particle size; 3. Designing and building a crusher capable of operating on very small quantities of mineral, if necessary on single crystals, and in such fashion as to minimize handling losses of material. Complete experiments have been carried out with massive quartz and individual quartz crystals. partial experiments, lacking surface measurements, have been made with glass spheres, galena, sphalerite, fluo-rite, salt and coal. Introduction The existence of regularity in weight distribution with size was noted many years ago, especially by A. 0. Gates;' the subject was also studied in detail by one of us.6 In the latter paper it was shown that rocks can be divided into two classes: homogeneous rocks, which show no preferential breaking, and heterogeneous rocks, which show preferential breaking at the grain size of the rock. It was shown, furthermore, that the fragments obtained by rupturing a homogeneous rock occur (in the fine range) in such abundance as to permit the writing of a relatively simple equation to relate the weight retained on a screen to the screen opening. With screens of which the openings are in constant ratio, the weight retained, w, is related to the screen size x by the equation w = Cxm [I] In this equation C and m are experimental constants. A plot of weight retained against particle size is a straight line of slope m if the scales for x and w are both logarithmic. In the fine range, the slopes of the size-distribution graphs plotted according to the method described above vary within a limited range. An inspection of a number of size-distribution data by various experimenters indicates that the slope very seldom exceeds 1.0, but is usually greater than 0.7. More recently, schuhmann8 proposed a method of charting that has so many advantages of its own that it has been used primarily in this work. For fine particles Schuhmann has found that the data are represented by the equation (x)m k [2]

Jan 1, 1947

By A. M. Gaudin, R. T. Hukki

Previous work on the principles of comminution has shown: (I) that the surface produced is proportional to work input (Rittinger law,1a-3); (2) that there is regularity to the weight distribution of the fragments according to size.4-10 In this paper it is brought out that the surface on the fragments is distributed in definite and simple relation to size. The experimental work has involved: I. Construction of an apparatus capable of measuring the surface of mineral fragments independently of the chemical composition of the fragments and independently of the site of the surface; 2. Refining the methods available for measurement of particle size; 3. Designing and building a crusher capable of operating on very small quantities of mineral, if necessary on single crystals, and in such fashion as to minimize handling losses of material. Complete experiments have been carried out with massive quartz and individual quartz crystals. partial experiments, lacking surface measurements, have been made with glass spheres, galena, sphalerite, fluo-rite, salt and coal. Introduction The existence of regularity in weight distribution with size was noted many years ago, especially by A. 0. Gates;' the subject was also studied in detail by one of us.6 In the latter paper it was shown that rocks can be divided into two classes: homogeneous rocks, which show no preferential breaking, and heterogeneous rocks, which show preferential breaking at the grain size of the rock. It was shown, furthermore, that the fragments obtained by rupturing a homogeneous rock occur (in the fine range) in such abundance as to permit the writing of a relatively simple equation to relate the weight retained on a screen to the screen opening. With screens of which the openings are in constant ratio, the weight retained, w, is related to the screen size x by the equation w = Cxm [I] In this equation C and m are experimental constants. A plot of weight retained against particle size is a straight line of slope m if the scales for x and w are both logarithmic. In the fine range, the slopes of the size-distribution graphs plotted according to the method described above vary within a limited range. An inspection of a number of size-distribution data by various experimenters indicates that the slope very seldom exceeds 1.0, but is usually greater than 0.7. More recently, schuhmann8 proposed a method of charting that has so many advantages of its own that it has been used primarily in this work. For fine particles Schuhmann has found that the data are represented by the equation (x)m k [2]

Jan 1, 1947

By Norman Pilling

THE solubilities of a series of experimental alloys covering the range 0 to 100 per cent. Ni, 0 to 30 per cent. Cr have been studied under conditions of complete submersion in several fully aerated acid solutions, and in solutions containing sulfurous acid. In nonoxidizing, hydrogen-discharging acids, if the nickel content is below a certain critical amount, chromium increases the rate of solution and nickel decreases this rate; this critical content of nickel is about 13 per cent. Alloys containing more than this corrode at a constant minimum rate independent of iron, nickel or chromium contents. Austenitic chrome-nickel steels may thus have a resistance to these acids equal to that of nickel-chromium alloys. In nitric acid and in unaerated sulfurous acid rather sharp limits of attack occur which are principally dependent on chromium content. In the former the limit of attack is not related to a particular chromium content but varies continuously with acid concentration. The action of sulfurous acid on these alloys is highly dependent on the presence of small amounts of other substances in solution, and many sulfurous acid mixtures rapidly attack alloys to which the pure acid is wholly inert. The observed effects are. not compatible with Tammann's theory relating corrosion resistance to lattice structure but are believed to be concordant with current views of the electrochemical nature of corrosion.

Jan 1, 1929

Jan 1, 1921

By J. L. Rodda, M. L. Fuller

In connection with an investigation in this laboratory on the high-zinc side of the copper-zinc system, it was observed that well developed segregate structures of the Widmansttten type were formed when a secondary phase precipitated from the solid solution of copper in zinc. This paper presents an analysis of the crystallographic relationship between the segregate and the solid solution matrix. The data to be presented are an interesting addition to the literature on segregate structures in that the plane of segregation is one of the less densely populated planes. In agreement with the generalization of C. H. Mathewson and D. W. Smith' the plane of segregation in the matrix contains the direction of closest atomic packing of the lattice. Furthermore, the matrix and the segregate are both hexagonal close-packed, which has not been reported hitherto in the 1iternture.l The increasing commercial importance of zinc alloys containing copper makes this fundamental study of value to the metallography of zinc alloys. Zinoeich Copper-zinc Alloys Copper enters into solid solution with zinc to at least 1.8 per cent at 400" C., according to W. M. Peirce.3 The solubility is less at lower temperatures. Thus a solid solution of copper in zinc, saturated at an elevated temperature, will precipitate the excess copper in a separate phase at a lower temperature, conditions of concentration, time, and temperature being suitable. The nature of these two phases has been established by the X-ray method of crystal analysis. Westgren and Phmgmén4 and also Owen and Preston5 have shown that the solid solution eta (7) is of the substitu-tional type with copper atoms replacing zinc atoms on the hexagonal

Jan 1, 1933

By W. H. Nielson, L. S. Diaz

Several techniques are presented to adjust small errors inherent in data collected from material balance measurements on the flotation process. The basic technique used is a Lagrange multiplier adjustment of the filtered data taken from the equipment measurements. The raw data are adjusted such that material balances are closed. The adjustments to each data point is inversely proportional to the square of the standard error of measurement. Problem areas in equipment utilization are discussed. Typical results from on-line measurements are presented. This technique can be applied to either on-line process measurements or metallurgical test data.

Jan 1, 1973

By H. Bartholomew, L. Bernstein

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

Jan 1, 1967