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By Leon W. Dupuy

A brief elemental discussion of the fundamental factors involved in diamond drilling often fills a need, particularly when a mine operator is contemplating for the first time an exploratory drilling campaign. Mr. James A. Barr, of the Mining Methods Committee of the Institute, has suggested that many engineers must undertake a drilling program of one kid or another and, in the case of diamond drilling, sometimes even are at a loss as to how to start correspondence. The Bureau of Mines has acquired much experience in managing exploratory diamond-drilling activities. Its activities in diamond drilling included exploring for potash in Texas, Utah and New Mexico1-' during the 1920's. The Strategic Minerals Exploration program was started in 1939 and was materially expanded during the war to include critical and essential minerals. At the peak of its war-time activity more than 200 engineers were employed, a majority of whom supervised diamond drilling. Many of them had little experience with such work prior to their employment with the Bureau, and it was necessary to instruct them in their duties. The purpose of this paper, therefore, is to present the fundamentals of exploratory diamond drilling from the viewpoint of management in such a way that they will Serve as a basis on which those beginning exploratory diamond drilling may build an experience and acquire ability to direct exploration as they gain that experience. Selection of Method of Drilling Selection of the method of drilling is governed by the type of material to be penetrated and by the type of sample needed to determine the quality and importance of a deposit. Types of drills that might be used for a given job include diamond drills, churn drills, hand auger drills, power auger drills, bucket drills, and rotary drills (sometimes called "seismograph rigs"). Each type has a specific field in which it is most useful. While the Bureau of Mines utilized all the types of drilling mentioned, diamond drilling was used on a majority of its exploratory projects. Factors Governing Selection of Diamond Drilling The prime consideration in selecting a method of drilling is first to determine what results are desired and then to choose a method that will furnish reliable data in the ground to be penetrated. Use of diamond drills permits recovery of a core as well as sludge at a comparatively low cost. The core provides an excellent means of studying the formation being drilled and furnishes much information that would be difficult to obtain otherwise. Diamond drills will recover a satis-

Jan 1, 1948

By E. C. Rudolphy, M. E. Potter, J. R. Mitchell

The effects of 0.006 to 0.20 pet Sn ml the hot workability and the annealed mechanical properties were investigated for Types 302, 410, and 430 stainless steel. The hot workability of these steels was not significantly affected by their tin content within the range studied, although some effects on mechanical properties were noted. Apart from the effect of tin, optimum hot-working temperatures and V-notch Charpy impact transition temperatures for these grades were determined. HIGH tin residuals in some heats of stainless steel have been blamed for the poor hot workability, particularly during secondary mill rolling. However, very little quantitative information has been available. Previous work1"6 with carbon steels indicates that tin increases tensile strength and hardness but de- creases tensile and impact ductility. Halley,7 in reviewing the sources and effects of residual elements in carbon and alloy steels, concluded that much of the surface checking (hot shortness) encountered in rolling was caused by copper, and that tin, arsenic, and antimony combined with copper to form low-melting constituents which further increase the steel's sensitivity to hot shortness. These elements had little effect in the absence of copper. A more recent paper by Langenberg and Johnson8 concluded that tin reduces hot workability but that researchers disagree concerning the amounts which will cause trouble. They state that laboratory investigations with small ingots seem to indicate a higher tolerable level of tin than do statistical studies of mill data, and also that statistical analysis of mill data indicate that small amounts of residual tin are detrimental to the surface quality of stainless sheet. The accumulative increase in the general level of tin and other tramp elements in steelmaking materials will present greater problems to steelmakers in the future. The purpose of the present study was to obtain quantitative information on the specific effects of tin on the hot workability and mechanical properties of such common stainless steels as Types 302, 410, and 430.

Jan 1, 1962

By L. S. Austin

Our SUCCESSFUL plants in the West were at first erected on a small scale, and as their business has been built up, have been added to gradually as their limitations permitted. They have had to adapt themselves later to their circumetances, making the best of drawbacks, and putting up with much which, had it been originally allowed for, would not now impede them.

Jan 1, 1897

By R. L. Boyer, F. Morgan, M. Muskat

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-' In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By M. Muskat, R. L. Boyer, F. Morgan

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-' In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By H. T. Mercer, A. C. Paulson

The composition of steel and the theory of its heat treatment have been so ably discussed elsewhere that it is unnecessary to go into the subject here. The purpose of this paper is to describe briefly the method of treating drill steel at the Copper Range mines, giving some of the troubles encountered and the manner in which they were overcome or corrected. To study the matter properly, it was necessary to devise a system of records that would show the actual underground performance of the drills. To illustrate this system, the records of the Champion mine are used, as it is at this mine that most of the work along these lines has been done. Reports from each drill machine are made daily by the shop and mine, and tables compiled from these reports show the footage drilled, steel broken, drills received and sent out at the shop, drills sharpened, and bits cut off. These data show what each machine or party is doing and whether the miners' supply of drills is kept up to date. There have been times when the supply of drills has been short and time lost by the miner in looking for drills. The daily records show the number and condition of drills on hand at all times. Under the old method of sharpening, the drills were heated in a coke furnace, the proper degree of heat being judged by color. Then they were sharpened in a machine, reheated in a second coke furnace where the proper heat was again determined by color, and quenched in water. While this method was fairly successful in the hands of a careful workman and for the solid steel used in the old piston drill machine, the introduction of the faster water machine, using hollow steel, produced changes both underground and in the shop. Much more was expected of the hollow-steel and hammer-type machine, with its improved method of rotation, but troubles due to breakage, burnt bits, uneven tempering, etc., at once appeared.

Jan 1, 1922

By H. T. Mercer

THE composition of steel and the theory of its heat treatment have been so ably discussed elsewhere that it is unnecessary to go into the subject here. The purpose of this paper is to describe briefly the method of treating drill steel at the Copper Range mines, giving some of the troubles encountered and the manner in which they were overcome or corrected. To study the matter properly, it was necessary to devise a system of records that would show the actual underground performance of the drills. To illustrate this system, the records of the Champion mine are used, as it is at this mine that most of the work along these lines has been done. Reports from each drill machine are made daily by the shop and mine, and tables compiled from these reports show the footage drilled, steel broken, drills received and sent out at the shop, drills sharpened, and bits cut off. These data show what each machine or party is doing and whether the miners' supply of drills is kept up to date. There have been times when the supply of drills has been short and time lost by the miner in looking for drills. The daily records show the number and condition of drills on hand at all times. Under the old method of sharpening, the drills were heated in a coke furnace, the proper degree of heat being judged by color. Then they were sharpened in a word drill-sharpening machine, reheated in a second coke furnace where the proper heat was again determined by color, and quenched in water. While this method was fairly successful in the hands of a careful workman and for the solid steel used in the old piston drill machine, the introduction of the faster water machine, using hollow steel, produced changes both underground and in the shop. Much more was expected of the hollow-steel and' hammer-type machine, with its improved method of rotation, but troubles due to breakage, burnt bits, uneven tempering, etc., at once began to appear.

Jan 8, 1920

By R. W. Hunt

The old plan was to increase every part of a rail much in the same proportion. But each part should be in proportion to what it ha.; to do. The head should be deep in proportion to tile amount. of traffic and the lowness of the rate of interest on its cost. The body need only he strong enough to carry the head after it is well worn down, and that deperlds on the weight of the machinery, and in the case of steel has little to do with the volume of traffic, except SO far as that affects weight of machinery. Ad on most railroad systems, the same niacliinery is used on main lines with heavy traffic, and bra11ct:es with light, I suggested in 1874 that each systern adopt the same body of rail for both, and make the head deeper on the main lines, shallower on the branches. This plan was adopted on the Pennsylvania Railroad. Bandberg seems to recognize this in his patterns of 1878. E. W. HUNT, TRoy, N. Y.: Again Dr. Dudley preaents to our cousideration a series of most carefully conductetl experiments, and ~llile I fully appreciate the labor and thought this work has cost him, I must still hesitate to accept his deductiono. This paper dilliirs from the previous one in that it denls esclrieively with the wearing qualitiei. of steel rails. Dr. Dudley gives his reason for this change in the following statement: " With the improvement in maintenance of way which has characterized the Pennsylvania Railroad during the last five or six yearn, the remova1 of rails from the track from the first two of these causes (i. e., broken and crushel), has, if I am right, quite notably diminished. This certainly is true with regard to broken rails. And if, as time advances, the number of crushed rails shall diminish, both because of the continued improvement in maintenance of way before referred to, and because, owing to improved and better methods at the steel works, there are fewer crushed rails caused by physical defects in the steel, the question of the wearing capacity of steel rails obviously becomes the allimportant one." Certainly the condition of the roadhd has much to do with mils brealring, crushing, and wearing. If the Pennsylvania and other railroads have done and are doing their part, Dr. Dudley oourteously admits that the steel works have performed part of theirs. But as far as I am informed, the formulas which they have used have been and are still quite wide of the one he continues to recommend. The rails which are not breaking or crushing to so great an extent as formerly, contain higher percentages of both carbon and manganese.

Jan 1, 1881

By R. H. Ernst, H. R. Ogden, D. J. Maykuth

AT present, no theories exist which allow prediction of the effect of alloying additions on the thermoelectric properties of metals. Nevertheless, Battelle and others1 have observed that, at high temperatures, the peak thermal electromotive-force output (relative to a platinum standard) occurs with metals in Group VI of the Periodic Chart. The authors suspected that this peak was associated with the fact that maximum electronic bond stability is achieved with these metals which have six bonding electrons per atom. On the basis of current electron-concentration theory for transition metals and alloys:' it was surmised that the addition of valency electrons to metals of Groups IV and V (accomplished by the addition of metals from Groups VI, VII, or VIII) should progressively increase the thermoelectric-power output of the resulting alloys until an alloy composition is reached at which the number of valency electrons per atom is six. A further increase in the ratio of valency electrons per atom should then decrease the thermoelectric power. In contrast, the addition of bonding electrons to Group VI, VII, or VIII metals should decrease their thermoelectric power since the electron per atom

Jan 1, 1965

By K. Matsuda, H. Tanaka, M. Mamiya, H. Majima

Copper cementation was studied from both thermodynamic and kinetic aspects. The temperature effect of copper cementation, which has been recognized as an anomalous result, and the rate enhancement phenomenon observed after the initial linear step are, in particular, focused in this work. The main results obtained are as follows; 1) Free energy changes of copper cementation reactions, calculated by the use of the "Correspondence Principle" of Criss and Cobble are rather insensitive to temperature. 2) A Flow-cell assembly consisting of a special cupric ion electrode, a calomel electrode and a potentiometer is particularly useful for the continuous measurements of copper cementation rate. 3) Two first-order reaction rate constants for the CU2+- Fe system were successfully determined by the use of the flow-cell assembly. 4) Activation energies determined for the initial rate and the 9 maximum rate of CU2+ - Fe system are both 4.6 kcal/mole. This fact suggests that the mechanisms of the initial reaction and the final reaction are essentially the same and both reactions are rate controlled by the diffusion in a boundary layer. The difference in the rate constants of them may fie explained by the effect of the nature of surface deposits. 5) Qualitative explanation of the rate enhancement phenomenon from the initial rate was successfully made by applying Bockris "Penetration Model."

Jan 1, 1976

By L. Casagrande, C. O. Brawner, D. L. Pentz, B. Kennedy, E. Hoek, H. Q. Golder, K. Barron

H. L. HAMMERSLEY, B. C. Dept. of Mines. I would like to ask Mr. Brawner if the direction that he measured in the boreholes with the camera was referenced to magnetic north? MR. BRAWNER. Yes, it was. However, there is one problem that you may encounter if the ore body is magnetic; the borehole compass will give erroneous results. Three procedures are available to overcome this. The first one involves the use of a gyro compass instead of a magnetic compass. The second technique developed by Christiansen in Salt Lake City, is to orient the core with the use of scribing knives. The third method is to remove the compass needle and place a steel ball in the compass case. The hole must be drilled at a slight angle off the vertical. The location of the steel ball, which will roll to the underside of the hole is photographed. A borehole directional survey is then made, from which the bearing of the steel ball relative to the axis of the compass can be determined. The joint orientation is then related to this bearing at all depths. J. ROBINSON, B. C. Dept. of Mines. It was stated this morning that there have been some recent developments that give us the ability to drill horizontal drainage holes and install drainage pipes more cheaply than in the past. Would Mr. Brawner tell us some of the new developments and methods of installing these horizontal drain holes? MR. BRAWNER There are two zones in which you may be concerned about installing drains; the first is in the overburden soil, the second is in the rock. Each area requires a different installation method. If the rock is fairly massive and the holes will remain open, the simplest procedure is to use standard air track equipment or a percussion drill. At one of the mines in the Highland Valley, drains up to 300 ft. long have been installed with a percussion drill at a rate of one drain per day. The costs were in the order of $2.30 and $2.40 per foot. If the rock is quite soft, such as in a serpentine, it will be necessary to install a casing in the hole. The least expensive casing that will not deteriorate within the life required should be used. Plastic pipe or black iron pipe are commonly used. In soft rock, it may be necessary to drill with a casing to prevent the col-

Jan 1, 1971

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By S. C. Sun, John A. L. Campbell

Objective of the ittvestigation was to determine the electrokinetic differences, if ally, of anthracite lithotypes and thus establish the feasibility of making a coqlstituent separation by froth flotation or other surface-dependent processes. The elec-trokinetic properties were determined by streaming potential methods. In addition, chemical and physical analyses of the lithotypes were made to establish nonsubjec-tive parameters for their diflerentiation. Electrokinetic results indicate a difference in the characteristics of the lithotypes. The isoelectric points of 4 anthracites and 12 lithotypes were obtained. It was suggested that the relative flotation rates of the lithotypes were pH dependent and that the maximum flotation rate of anthracite occurs in an acidic circuit. Although there has been an increased interest in the electrokinetic properties of coal,' research on the subject is still in an early stage of development."' To the authors' knowledge, no electrokinetic studies have been made on coal lithotypes, particularly anthracite litho-types. This paper presents the results of an investigation of the double layer properties displayed at the anthracite/water interface (whole coal and lithotypes) as determined by streaming potential methods. It is hoped that this investigation and related future investigations will provide correlations from which the surface properties of any coal can be predicted and then related to surface-dependent processes such as froth flotation and flocculation. Another aspect of this research, undertaken to determine the physical and chemical parameters necessary for anthracite lithotype differentiation, was previously published.? The number of parameters involved, lithologic, organic and inorganic, and the wide divergence of these parameters within an individual coal limits the practical utilization of the results; however, the result? are of value and of interest in guiding theoretical developments. Keeping the limitations in mind, the results are analyzed in terms of their application to froth flotation processes and are used to indicate the feasibility of making a lithotype separation by flotation. Experimental Procedure Prior to discussing the experimental work per se, it would be of value to establish an understanding of anthracite lithology. Anthracite Lithology: Coal seams display two different modes of variation, rank and type. A coal's position in the continuous series ranging from peats through anthracites determines its rank. The rank of the material under consideration is anthracite. The different bands of coal which constitute a coal seam are distinctly contrasted in regard to physical properties and chemical composition. These megascopic bands are the coal types and are termed lithotypes., A megascopic examination of 11 anthracites revealed three distinct, homogeneous, lithotypes. The classic description of bituminous coal lithotypes as proposed by Stope" was found to be quite adequate for recognizing the three lithotypes in anthracite, namely vitrain, durain, and fusain. The term vitrain describes the brilliant constituent of coal; durain describes dull coal; and fusain is the term applied to fossil charcoal. The anthracites studied were generally found to contain 60-80% vitrain, 10-30% durain, and 1-10% fusain. A complete description of the physical characteristics and chemical composition of the studied lithotypes can be found in a previous publication.' Sample Preparation: Nine of the anthracites used in the investigation were from Pennsylvania, one was from Russia, and one from Wales. Table 1 shows the various designations and sources of the employed anthracites. The letter V, D, or F added to the whole coal designation indicates respectively the vitrain, durain or fusain lithotype of that coal. The samples were carefully collected to avoid contamination. To insure against oxidation, the samples were obtained as fresh as possible and stored under nitrogen or water. Generally a representative sample of the seam and samples containing high concentrations of one or another of the petrographic constituents were secured for each coal. Pure lithotypes were prepared by manual separation and selection. The pure lithotypes and representative samples were ground to —35 mesh and screened to 35 x 48 mesh. The 35 x 48-mesh fraction was then passed over a magnet to remove iron contamination, washed with doubly

Jan 1, 1971

By R. S. Dean

THE commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in MINING AND METALLURGY for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for "the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. PRACTICE AT BOULDER CITY The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: I. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By Michael B. Bever, Carl F. Floe

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By Carl F. Floe, Michael B. Bever

The solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to I300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. Review of Previous Work The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar5 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwasé3 reported large hydrogen solubility values for several compositions of copper-tin alloys, which appear to be in error.

Jan 1, 1944

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By E. T. Turkdogan, L. S. Darken

Using the quadratic formalism, thermodynamic equations are derived for the composition dependence of the heat and entropy of mixing. The applicability of these equations is confirmed by available experimental data on the activities and heats of mixing for binary metallic systems of Group ZZB elements. In a recent paper arkeen' introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. That is, in the terminal region, which may extend to as much as 60 at. pct, the logarithm of the activity coefficient, log y,, of component 2 is a linear function of (1 - N,)' where N2 is the atom fraction of component 2. Similarly, for the other component, log yl is a linear function of (1 - N,)'. A number of iron-base binary liquid alloys were shown to obey this quadratic formalism. arkeen' extended this formalism also to any corner of a ternary system and showed that the activity coefficients of the components 1, 2 and 3 (1 is taken as the solvent) can be represented by quadratic terms involving five parameters, four of the binaries and one for the ternary system. Numerous examples given by arkeen' demonstrated the general applicability of the quadratic formalism to iron-base systems over a wide composition range. In this paper further examples are given of binary liquid systems (Group IIB elements, Zn, Cd, and Hg) and of several solid solutions, again demonstrating the appropriateness of this concept. A further purpose of this paper is to extend the quadratic formalism to the enthalpy and excess entropy of binary metallic solutions and to test the equations so found using available experimental data. QUADRATIC FORMALISM FOR HEATS AND ENTROPIES OF MIXING OF BINARY METALLIC SOLUTIONS The following equations, reproduced from Darken's paper, are for the two terminal regions of binary systems. at infinite dilution and a's are temperature dependent parameters to be determined from the experimental data. Although the quadratic formalism is an assumed representation of the data, Eqs. [I] to [4] are thermo-dynamically consistent with the Gibbs-Duhem relation and satisfy Raoult's and Henry's laws as limiting cases. As pointed out previously,' the following form of the Gibbs-Duhem equation facilitates the integration in general but particularly in regions I and 11, where each of the derivatives is constant. The partial molar enthalpy of solution i, (and i; the value of i, at infinite dilution) are related to the activity coefficients y, and y," by the thermodynamic relation Differentiating Eq. [l ] with respect to 1/T and substituting the above thermodynamic relation gives for region (I) It is reasonable to assume that over a temperature range of experimental interest, the enthalpy of mixing is essentially independent of temperature, implying from Eq. [7] that the derivative da,,/d(l/) is also independent of temperature. On the basis of this argument, the temperature dependence of a has the form where £ and S have the units of enthalpy and entropy respectively; they are characteristic parameters for a terminal region of a binary system, e.g. for region (I), C12, S12 and for region (II), d:,,, S2,. Using this equation gives for dff ,/ d(l/), From Eqs. [7] and [9] an expre_ssion is obtained for the composition dependence of L,. Similar calculations are made for El and the results are summarized below for the two terminal regions. For region (I), The corresponding expressions for the molar heat of solution, AHM, are readily obtained from the above equations for the two terminal regions: For region (I),

Jan 1, 1969

By Carl F. Floe, Michael B. Bever

TRE solubility of hydrogen in molten copper-tin alloys is of both practical and theoretical interest. From a practical standpoint, data on the equilibrium solubility as a function of temperature, pressure and alloy composition are valuable for a better understanding of porosity problems in bronze castings. From the theoretical point of view the determination of the hydrogen-copper-tin equilibrium is of interest since it extends the laws governing the solution of gases in metals. This paper presents the results of an investigation of the solubility of hydrogen in representative compositions of the copper-tin system at temperatures ranging from above the liquidus to 1300°C. and at pressures from less than 50 mm. of mercury to about atmospheric. REVIEW OF PREVIOUS WORK The solubility of hydrogen in copper was determined by Sieverts and Krumbhaarl in 1910 and by Roentgen and Moeller2 in 1934. Their values are in fair agreement. In 1926 Iwasé3 reported results that were very much higher. The published data on the solubility of hydrogen in tin do not agree. Smithells4 states that no reliable data are available. According to Sieverts and Krumbhaar,5 hydrogen is insoluble in tin. Bircumshaw,6 on the other hand, found a definite solubility at 800°C. The latter's experimental procedure did not provide for stirring of the metal and in his opinion he failed to reach equilibrium. Iwasé3 again reported large solubility values. For copper alloys, Sieverts and Krumbhaar6 distinguished between alloying elements that do not markedly affect the solubility of hydrogen, elements that increase the solubility, and elements that reduce it. They named gold, tin, and aluminum as examples of this last group and reported hydrogen solubility data at 1225°C. for the copper-rich side of these alloy systems at atmospheric pressure. Without giving experimental results, they stated that the amount of hydrogen dissolved by liquid copper alloys is proportional to the square root of the pressure as in pure metals. These authors suggested that in a limited way the effect of an alloying element on the solubility of a gas is related to the constitution diagram for the alloy system. Sieverts7 also called attention to the fact that the curve of hydrogen solubility versus composition of copper-tin alloys shows a sharp change of direction at the composition of Cu3Sn and suggested that this compound persists at least to some extent in the molten state. Iwas3é reported large hydrogen solubility values for several compositions of copper- tin alloys, which appear to be in error.

Jan 1, 1944