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By John Rogers

The goal of a detailed quantitative understanding of the variables insulfide flotation in terms of established, or new, scientific principles is still distant, although there has been a good beginning in the past 50 years with more rapid progress since 1930. Advances have paralleled closely those in other branches of surface chemistry and the development of a series of experimental techniques such as contact angle, surface area measurement, radioactive tracers, infrared spectra, electron diffraction, monolayer, and electro- chemical methods of investigation. The second editions of books by Sutherland and Warkl ( 1955) and Gaudin2 ( 19571, are detailed accounts of this progress. The complexity of sulfide mineral flotation systems is indicated by Sutherland and Warkl who list 32 variables of flotation, of which only 22 can usually be controlled by the metallurgist. A consequence of this multiplicity of variables, many of which may be specific to each particular ore, is that ways of floating sulfide minerals from new ores are still developed empirically. How- ever, this review will try to show how the chemistry of the function of frothers, collectors, depressants, and activators in sulfide flotation is being steadily unravelled. Chiefly, it will be concerned with the interaction of pure soluble compounds with individual sulfide minerals, the surfaces of which are often not stoichiometric for several reasons discussed by Plaksin.3 As a result, for example, a freshly cleaved galena surface has cathodic and anodic areas which have different degrees of oxidation and different reactivity to- wards collectors like xanthate. Such complicating considerations should be remembered in the subsequent discussion of pure minerals. THE NEED FOR FLOTATION REAGENTS After considerable controversy it has been established with a few exceptions that unoxidized, uncontaminated sulfides will not float. Moreover all flotation plants recovering sulfide minerals use collectors which are removed from the circuit with the sulfides. Gaudin, Miaw, and Spedden4 have discussed the relation between the crystal structure of solids and the native floatability of the exceptions mentioned above. A second question which has been much explored is the nature of the surface on which a collector like xanthate is adsorbed or reacts. Is this the un- changed surface of the sulfide mineral, or does the adsorption depend on the initial oxidation of the sulfide surface ? Sutherland and Warkl and Gaudin2 discuss the work of Taggart5 and others on this question without reaching any other conclusion than that oxygen was important.

Jan 1, 1962

By Marcel R. Daly

EUGENE COSTS, Calgary, Alberta (communication to the Secretary*).¬This new theory to account for the accumulation of commercial deposits of oil and gas, is deliberately and admittedly based on the hypothesis that the origin of these products is organic. Mr. Daly says (page 1142), "Should the organic origin of the petroleum that is found in pools be granted, the following interpretation is offered for the mechanics of its accumulation." But suppose the origin thus accepted by definition be incorrect, then what becomes of the diastrophic theory, Mr. Daly's interpretation? As Mr. Daly remarks himself (same page), "It is obvious that the history of petroleum will have to be entirely different, dependent upon its origin, either from emanations coming from the depths, or from organic decomposition in the strata themselves." Then why should one propound a theory, through which he is endeavoring to trace the history of petroleum, by starting with a definition of its origin? The origin should be the deduction, the forced conclusion of the theory, and not its starting point. Facts alone should be considered first, in any theory worth the name, until sufficient proofs have accumulated to permit of the deduction of a complete explanation for these facts. This would lead one to the origin through a real theory founded on facts, and not based on a preconceived idea perhaps true, but possibly fanciful. Mr. Daly's way can only lead on one road, namely the organic road, and, I repeat, it may be the wrong road. In the case of the petroleum deposits, as .I have endeavored to show in several papers on the subject, to which the reader may refer, the facts clearly lead to the force conclusion that their origin is not one of accumulations of hydrocarbons at first disseminated in the sedimentary strata but the reverse process of subsequent local infiltrations and impregnations of hydrocarbon emanations from the depths. This new theory, therefore, founded on, an erroneous conception of origin cannot be a help in the solution of the petroleum' problem, not any more than were the anti-theory or the hydraulic theory, both of which were also based on the same error, although Mr. Daly is inclined to think that the authors of these two theories did not accept the misconception boldly enough (page 1142). -

Jan 12, 1916

THE great subject of interest in American affairs during February was the consideration of the proposed soldier bonus. This proposal was based upon the idea that, because most of the workers of the United States had enjoyed high wages during war, the soldiers were entitled to "adjusted compensa-tion" in order to equalize things. It overlooked the fact that the soldiers, themselves, had the opportunity to enjoy high wages in 1919 and 1920, when rates were highest. Apart from this, the whole project was founded on fallacies and involved what would be nothing less than economic crime. Although it looked as if the measure were destined to be railroaded through Congress, so great a storm of protest was pelted upon Congress that the present outlook is that the whole project will be abandoned. There was probably some increase in the physical volume of business during February. A rise in prices for agricultural products assisted the farmers mate-rially. These developments, however, are not to be construed as presaging any general upward movement. On the contrary, the current year is to be contem-plated as one of serious labor troubles, following inevit-able reductions of wages. These began in February in the form of an extensive strike in the cotton textile industry of New England, accompanied by some rioting in Rhode Island. The coal miners have had numerous conferences, without coming to any encouraging results, and the stage appears to be fully set for a general strike beginning Apr. 1. About the only question now is whether this will comprise both the bituminous and anthracite miners. If the latter refuse to go out, no serious shortage of coal is anticipated, the belief being that the existing stocks together with the output of the non-union mines will supply the demand, which is sub-normal even now. In the metal industries, lead and zinc were dull but stable. The weakening tendency in iron and steel that was manifest during January appeared to be checked, at least temporarily. Copper was charac-terized by a distinct weakness and a considerable decline in the market. This downward movement was inspired by the news during January that several of the important mining companies were taking steps to resume production. During February the demand for copper, both foreign and domestic, was poor.

Jan 3, 1922

The primary purpose of the Institute is to advance the technologic and engineering arts embraced by it through interchange of knowledge. This can best be clone by the presentation and discussion of technical papers by its members. Short practical papers are especially welcome. An author should always satisfy himself that his material is of a quality that will he a credit to him and to the Institute. The preparation of a good paper frequently leads to a reorientation of the author's thoughts, and publication contributes much to the professional standing of the author. Members are urged to submit papers presenting the results of their work. Attention to the following suggestions will greatly further the prompt and efficient handling of manuscripts. 1. SUBJECTS: The subject must be within the field of the Institute. Original work, the results of field, plant, laboratory or theoretical investigations, new views on old but important problems and occasionally reviews of timely and important subjects of wide interest to our members may constitute the basis of a paper. The mere fact that the work is original does not necessarily justify publication: it must be of a substantial nature, of value to a reasonable number of our members and worthy of permanent record. It is seldom desirable to subdivide the results of a single research for publication in a variety of journals. Previous publication is usually a bar to acceptance. If any part of your paper has been published elsewhere and you regard repetition as absolutely necessary please so state in your covering letter. 2. CONSTRUCTION: Papers should be clearly and concisely written in good English. Care in this regard ensures wider reading and the saving in space permits the Institute to publish more papers. It is the experience of the Papers and Publications Committee that most papers can he improved by condensation. "Readers" who are asked to recommend acceptance or nonacceptance put particular emphasis on the length of the paper and the elimination of unnecessary or any extraneous material. The terminology and units employed should be those current in the particular field. An examination of Institute publications will afford useful guidance in such matters. Webster's New International Dictionary, 1935 edition, is the Institute's authority for spelling and style. Various abbreviations are used habitually; for instance, lb., pound; bbl., barrel or barrels; ft., foot or feet; hr., hour or hours; in., inch or inches; Fig. 1 but Figs. 2 and 3.

Jan 1, 1946

By B. B. Zavoico

The oil industry in the Soviet Union closed the 1929-1930 operating year fulfilling its assigned program. During this period of time, however, no basic improvements were noted within the industry. A careful study of the conditions indicates that disorganization in most branches increased continually; that supply and transportation problems are approaching a state of breakdown; that labor problems become increasingly difficult and that the estimates for 1931-1933 period are too large. The production of all Russian fields increased by 27,200,000 bbl., as compared with the 1928-1929 operating year, while the next year's program anticipates a further increase of 46,000,000 bbl., and the 1933 plans call for an amazing total of 330,000,000 bbl., or over 150 per cent, more than the production of the operating year that has just closed. Table 1 shows petroleum production in Russia by individual areas and fields from 1916, and furnishes estimates for the three coming years, which constitute the balance of the Five-year plan. A brief analysis of Table 1 will show that the Soviet Planning Commission anticipates that the fully developed fields of the Apsheron-Baku will double their production by 1933, .as compared with 1929-1930, and that the old Grozny fields, which are already showing a tendency to decline, will increase their output from 44,110,000 bbl. in 1929-1930 to 68,000,000 bbl. in 1933. Furthermore, in 1933 new fields are slated to produce not less than 100,000,000 bbl., a figure which even under most favorable conditions in Russia would be hard to achieve. Of course, Russia could develop such production, because the country is not lacking in the prospective reserves, but the transportation in the country today (as in the past.) is in such poor shape that neither the supply of a gigantic oil industry nor the movement of its products is within the realm of possibility. Table 1 shows the future estimated crude oil production as required by the Five-year plan, and also as reasonably estimated by the author, taking into account natural declines in old fields, slow development of new areas and the deficiency of the transport. While in the 1929-1930 operating year only two major fields underproduced (Surakany and Maikop) and the plan was fulfilled to the extent of 97.4 per cent., the production of the last three months of 1930 ("Shock Quarter") indicated

Jan 1, 1931

By R. G. Wheeler, J. W. Goffard

The Larson-Miller parameter was used to correlate time, temperature, and indentation creep of magnesium, aluminum, and some of their alloys. In the temperature range 300" to 450°C, the short-time Meyer hardness of pure magnesium was less than that of the magnesium alloys tested, but for long times the pure magnesium has greater indentation creep resistance. Aluminum (1100 alloy) had 1.5 to 2.5 times more indentation creep resistance than magnesium at 300" and 450oC, respectively. Hardening of aluminum with a dispersion of Al2O3 was effective in the time and temperature ranges studied. New technologies have required the development of new materials and the utilization of the more familiar materials for new and unusual applications. The use of magnesium and aluminum and some of their alloys, because of their desirable nuclear characteristics, light weight, low cost, and ready availability, has been extended to the 300" to 450°C temperature range. In this temperature range the basic consideration of these materials must be their rate of plastic flow rather than offset yield strengths. The indentation testing reported here arose from a need for design data for the load-holding ability of supports made of these materials. Test Procedure—Hardness indents were made with a 0.275-in.-diam quartz indentor and a 10.65-lb load. The indentor was made by fire-polishing a spherical surface on the end of a fused quartz rod. The samples were held at temperature in a graphite crucible controlled to ±2°C. A thermocouple was attached to the sample and test temperatures were recorded. The diameter of the spherical indentation was measured at the end of a test period and the compression stress (Meyer Hardness) was determined by: H___________load__________ m = projected area of indent Samples were 1 in. in diam and at least 1/4 in. thick. It was observed that at the higher temperatures and longer times, the quartz indentor would stick to the magnesium sample. The quartz indentor was, therefore, frequently inspected and fire-polishing repeated when necessary. The area of sticking was always a small fraction of the area of indent and was therefore considered to have an insignificant effect on results. Correlation of Hot-Indentation Test Data with Time-Temperature Parameter—Sherby and Dorn' have correlated creep or tensile data of a' solid solutions of aluminum with a temperature and strain-rate parameter suggested by Zener and Holloman. underwood2 used this parameter to correlate creep properties of some steels with hot hardness, and upon the basis of this correlation a means of obtaining creep properties from short-time (and inexpensive) hot hardness tests has been demonstrated. Since the validity of the correlation of creep properties with a time-temperature parameter and the correlation of creep properties with hot hardness have been shown, it follows that hot hardness may correlate with the time-temperature parameter. The hot-indentation data obtained was expressed as Meyer hardness, and was shown to be time and temperature dependent. Correlation of Meyer hardness, time, and temperature with the parameter was made using the relationship: Hm = Meyer hardness t = time, hours T = absolute temperature, OK K = constant A value for the constant K was calculated by equating In l/t + K/T at different temperatures and times but at the same hardness. The correlation was tested by plotting Hm vs the parameter, In 1/t +K/T. Since materials are being sought which have high hardness at low indentation creep, i.e., a high Meyer hardness for long time at high temperatures, low values of the parameter are ofthe most interest. TEST RESULTS Magnesium—Pure magnesium (99.98 pct) cut from extruded rod was indentation tested perpendicular to the rod axis at temperatures of 300°, 350°, 400°, and 450°C for times ranging from 6 sec to 112 hr. Fig. 1 shows the time dependency of Meyer hardness at the four constant temperatures. Fig. 2 shows the correlation of the Meyer hardness of pure magnesium with the time-temperature parameter using a K of 22,720 in Eq. [I]. At the bottom of Fig. 2, the effect of doubling the time of indentation t2 = 2(t1), on the abscissa for any time is shown graphically. This effect is of constant magnitude. Also shown graphically are the magnitudes of the effects on the

Jan 1, 1960

T. Kirke Rose, London, Eng. (communication to the Secretary*) :—The authors have shown that, under certain conditions, the rate of dissolution of gold by chlorine and bromine is reduced by the addition of 10 per cent. of silver to the gold, and that the action is almost stopped when the silver amounts to 30 or 40 per cent. of the alloy. Even if full recognition is given to the practical way in which the work was done, however, it is to be regretted that Prof. Hofman and Mr. Magnusou did not determine the temperature at which the experiments were carried out. From the details given, it may be inferred that the temperature was raised by chemical action by about 20' C. when 21 g. of sulphuric acid was added, and that the mixture was then slowly cooled down during the experiment. When bromine or very weak chlorine solutions were used, there could not have been any perceptible heating-action. As the action of both chlorine and bromine is aided by heat, it follows that the stronger solutions of chlorine were given an unfair advantage over the weaker solutions, and over bromine. If the temperature had been the same in each case, I do not think that the conclusions deduced by Prof. Hofman and Mr. Magnuson' would have been found to be justified. (This is speaking generally. In barrel-treatment the conditions are similar to those in the experiments.) The superior speed of bromine as compared with chlorine at equivalent strengths is not yet disproved, and the differences noted between strong and weak solutions of chlorine may have been largely a function of the temperature. Moreover, the authors used somewhat-coarse particles of gold, and did not try how far time was a factor, although it is obvi-

Jan 1, 1906

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,' the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275'C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By Leah L. Naugle, H. G. Landau, H. H. Lowry

EVIDENCE has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its "Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,1-12 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends-including coals numbered I to 55b, inclusive -which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or I8-in. cylindrical retorts." In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash; from 2.1 to 15.9 per cent, in moisture from o.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the go coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1941

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

By G. W. Healy, N. R. Griffing

The activity coefficient of sulfur in Cr-Fe-S melts was determined by measuring the values of Ph3Rh,in equilibrium with such melts. The results showed that chromium has a pronounced negative effect on the activity coefficient of sulfur, which up to about 20 pct Cr may be represented by the equation: log f; = - 0.019 pct Cr It was also found that the influence of chromium was not altered by the presence of appreciable amounts of carbon or silicon. The influence of alloying elements on the activity of sulfur in molten iron has been the subject of many investigations; however the effect of one important alloying element, chromium, has not been reported, and the object of the present investigation was to determine its effect on the activity coefficient of sulfur in liquid Fe-Cr-S alloys both in the absence and in the presence of carbon and/or silicon. EXPERIMENTAL PROCEDURE The general method employed consisted of passing mixtures of hydrogen and hydrogen sulfide over the sulfur-containing melt of interest and analyzing the outgoing gas to determine the equilibrium value of which resulted from the reaction shown in Eq. 111. H, (gas) + S (dissolved in melt) = H,S (gas) 111 The activity coefficient of sulfur, fs, was then calculated with Eq. [2] in which K, is the known equilibrium constant of Eq. [I] for dilute solutions of sulfur in iron. Raw materials used in the preparation of the charges included commercial grades of electrolytic iron and chromium and carbon-reduced, acid-treated silicon of 99.9 pct purity. Oxygen in the former presented no problem since it was removed by hydrogen in the normal course of an experiment. Carbon was added in the form of premelted iron-carbon and chromium-carbon master alloys. Sulfur was charged as iron sulfide prepared by first heating powdered iron and sulfur in air in an alumina dish until reaction occurred, and then deoxidizing by melting in a hydrogen atmosphere. Commercially bottled hydrogen and hydrogen sulfide were used after being passed through purification systems containing palladium, "Drierite," and magnesium perchlorate in the case of hydrogen, and "Drierite" alone in the case of hydrogen sulfide. Lamp-grade cylinder argon served as a flushing agent without further purification. Charges weighing from 300 to 500 g were placed in a high-purity alumina crucible of 0250-ml capacity and heated in an argon atmosphere in the induction-heated carbon-tube furnace illustrated in Fig. 1. During heating, a dry hydrogen atmosphere was substituted for argon in order that deoxidation of the charge and flushing out of argon would be accomplished sooner. After the charge melted, a Pt-Pt 10 pct Rh thermocouple contained in an alumina protection tube was immersed in the melt, and the desired melt temperature (usually 1600°C) was established. Higher temperatures up to 1760°C were required for some chromium-rich alloys because of their higher melting points, and in these cases a Pt 6 pct Rh-Pt 30 pct Rh thermocouple was used. The thermocouple output was fed to an automatic controller which provided straight line temperature

Jan 1, 1961

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

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

THE paper on "Cross-cuts in Coal Mining," by J. J. Rutledge (published in MINING AND METAL-LURGY, February, 1927, p. 64) was brought up for discussion at the annual meeting, where the follow-ing comments were made T. D. Thomas (Lehigh Coal & Navigation Co., Lansford, Pa.) : This question has caused me a lot of worry, not in the particular district in which I am, but throughout other districts. There are always several angles to consider. If you are in a hurry to push development work, you might increase the distance between cross-cuts from 60 to 350 ft., but if you have a 40-ft. chain pillar every 60 ft. it will cut down your entry driving a whole lot. Looking at it from the ventilation angle, I agree that too many cross-cuts in entries are bad things. You have a tremendous amount of leakage, and I have seen currents starting out with 45,000 cu. ft., and after passing about 30 or 40 cross-cuts the current has dwindled down to about 18,000 or 15;000 cu. ft. The result is that the question of putting in auxiliary fans is raised. That involves several points into which I do not want to go too far, but I am in favor of not getting in too many cross-cuts, putting them in only where they are necessary: I think the state mining laws are wrong in a number of places on that, and that when you finish with a cross-cut it should be in the room. It should be well sealed on an entry. There are several ways of tightening up the cross-cuts so as not to have the great amount of leakage and wastage of: air that we now have. 'I prefer tile stopping; other people prefer cement or brick, but there is a big fac-tor to all mines, saving the mine. I checked up on the number of fans in the anthracite region and found there are 651. That was derived from the state report of 1921, and it enabled me to compute from the power the weight of the air. In the anthracite region of Pennsylvania we put in 9 tons of air to every ton of coal we get out. Tracing that back again and taking the Government's figures which they made some time ago, I found but 20 per cent of the air got to the faces where it was actually needed. That is a tremendous big loss and shows a possibility for saving, money for the various coal companies. Chairman Rice: I think what Mr. Thomas refers to was an investigation by R. Y. Williams, of the Bureau of Mines in Illinois, where a study was made of 100 typical mines, and, speaking off-hand, my recollection is that we found as little as 15 per cent of air reached the faces in one of the mines and another was as much as 50. That seems to be a reflection on the type of stoppings and general ventilation scheme.

Jan 3, 1927

By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

This issue presents the first of several articles making up the Bump Symposium, which was held at the 1958 Annual Meeting of AIME. Other Symposium papers will appear in the September issue of Mining Engineering. THE term mountain bump describes the sudden rupture of one or more coal pillars under excessive stress. These bursts occur with varying degrees of violence and sometimes include adjacent strata, especially the bottom rock. Many failures do not develop enough violence to be dangerous and are regarded as an aid to coal production, but severe occurrences are accompanied by tons of flying coal, dense clouds of dust, and excessive gas emission. Such bursts sometimes throw heavy machinery several feet. Major factors to be considered in the problem are the nature of the strata above and below the seam and the depth of cover. Bumps are classified as to their nature, extent of damage, and point of occurrence, e. g., face bump, coal bump, high side bump, low side pavement bump, and district bump. The problem is extremely complex, and it cannot be over-emphasized that preventive measures, if they are to be successful, must be based on a thorough study of conditions in the individual mine. In western Canada, for example, the McGillivray mine, operating in a 9-ft seam at 2000 ft, has experienced severe bumps, but there have been no occurrences in the International mine, which operates in the same coal seam at 2400 ft, where the coal averages 17 ft thick. Differences in conditions governing the operation of these two mines are described in one of the following articles (see page 883). Again, most bumps in coal mines take place along pillar extraction lines, but at the Sunnyside mine in Utah they also occur a long way from active workings and sometimes in virgin territory. It is usual, too, for such failures to occur under fairly deep cover. But at Sunnyside, to cite only one instance, there have been disturbances along the main fault zone under less than 500 ft of cover. All too often conditions favorable to bumps are revealed only by actual mining—at Springhill No. 2 mine, drilling in roof and pavement strata disclosed a 60-ft sandstone bed after operations had started— and where extraction has advanced too far for preventive measures to be incorporated in the mining plan, districts have had to be abandoned. But in an era when premium ores are being rapidly depleted in the face of rising demands, abandonment is not easily justified. There must be systematic planning to eliminate coal mine bumps, insofar as this is possible. As in the Gary district of West Virginia (see page 888) much has been accomplished by planned operations based on known factors in bump control. But even this is not enough. Precise instrumentation is needed to indicate where bumps are likely to occur, and in both the U. S. and Canada stress analysis studies are being carried out with this object in view. These pages reveal the progress being made.

Jan 1, 1959

By B. B. Cox

Since our last review of Iraq,' considerable progress has been made not only in exploiting Iraq's potential resources but in building pipe lines to carry the oil to the Mediterranean. No new fields were discovered in 1933. The Naft Khaneh field, discovered in early 1927 by the Khaniqin Oil Co. (subsidiary of the Anglo-Persian Oil Co.), continues to supply the local markets through the Rafidain Oil Co. Kirkuk field, discovered by the Turkish Petroleum Co. Oct. 14, 1927, remained shut in pending the completion of the Mediterranean pipe lines, and the Qaiyarah field, discovered by the same company on Oct. 13,1927, was abandoned in 1928. The principal development of interest during the year was the progress made on construction of the Iraq Petroleum Company's 1152-mile pipe line from Kirkuk to the Mediterranean. The line is double 10-in. and 12-in. pipe for 156 miles west of Kirkuk, where the parallel lines bifurcate, one leg going through British mandated territory to the new port of Haifa and the other through French mandated Syria to Tripoli. Each line may be operated independently of the other. There are three double stations on the Kirkuk-Haditha portion, four single stations on the Tripoli leg, and five on the Haifa in addition to a relief station in the Jordan Valley. Except for the Jordan Valley section and two other short stretches on the Haifa leg where pressures are exceptionally high, the line is single. Sea loading lines will be used exclusively at Tripoli and both sea loading lines and dock loading will be employed at Haifa. All pipe was welded and buried before the end of December, 1933. It is anticipated that enough stations will be completed to make 50 per cent capacity operation possible some time during the latter half of the current year. Some months will then be required in which to fill the line, so that if terminal facilities are ready and no unexpected emergencies arise, partial daily deliveries of Iraq crude may be received at the Mediterranean some time during the final quarter of the current year. Capacity operation of 84,000 bbl. per day is not anticipated much before the middle of 1935. Oil and Gas Production No gas is produced commercially and, except for Naft Rhaneh production, no crude is marketed. Although the Turkish Petroleum Co. and

Jan 1, 1934

By J. E. Tobey

UNQUESTIONABLY, manufactured gas will stage a comeback of such huge proportions as to dwarf its previous history. Timing will depend on two things: the diminishing supply of natural gas and the perfecting of processes for large-scale production of high-Btu gas from, coal. What the timing will be, and how soon the new era will begin for manufactured gas, no one knows. It may be just around the corner and it may be several years, but it is certain to come. It will depend on economic changes, and any major world upheaval might accelerate it tremendously. Supplemental gas for pipelines will come no doubt from two sources at least: (1) synthetic-fuel plants of the coal-chemical group, which produce chemicals and liquid fuels with a tail gas high in methane as a by-product; and (2) large-scale gasification plants, which will produce high-Btu gas entirely or as a major product with chemicals and liquid fuels as by-products. There is important activity at the present time, in the development of new processes and the improvement of those now in existence. The first large-scale gasification plants of the second category probably will be strategically located in the coal fields on or near the long-distance transmission gas lines, and these plants probably will operate jointly with large natural gas storage fields. Inasmuch as virtually all the major gas-transmission lines cross one or more coal fields, such locations will not be difficult to find. It will be a practical necessity to produce a high-Btu gas -that is, 750 to 1000 Btu-in order to maintain the capacity of the main transmission lines and local city distribution systems and further to eliminate the problem of appliance changeovers in the cities. If gasification plants on a medium or smaller scale prove to be economical, local gas utilities no doubt will consider .the construction of such plants to supplement their supply of natural gas. If low-temperature distillation processes like those now being developed by the Pittsburgh Consolidation Coal Co. are successful, and there is reason to believe that they will be, utilities that supply both gas and electricity to communities would find this method particularly attractive, as they could burn the char product directly under power boilers, thereby minimizing thermal

Jan 1, 1953

By R. W. Raymond

(Reprinted With some additions and changes from the Engineering and Mining Journal)] THE death of Prof. Samuel Benedict Christy on the 30th of November,. at the age of 61 years, cuts short a brilliant and influential professional career. He was born in San Francisco, Aug. 8, 1853, and was graduated as Bachelor of Philosophy at the University of California in 1874. For the five years that followed, he studied mining and metallurgy as a post-graduate in the same institution, serving also as instructor in analytical chemistry, and becoming in 1879 instructor in mining and metallurgy¬a position which he held until 1885. During this period he became known also by his contributions to technical literature, the earliest of which, perhaps, was his report on the Monte Diablo coals (in 1875); but the first which drew my attention to him was an exceedingly able discussion (in 1879) of the genesis of the quicksilver deposits of California, in which he followed with much acuteness and originality the lead of Professor Becker, who had been teaching at the University of California. The notion of the thermo-aqueous formation of such deposits was then new; and the laborers in a field now familiar to every student deserve the credit due to pioneers. For some years the subject of quicksilver seems to have occupied much of Christy's attention. In 1877, he described the mines and works at Almaden, Spain; in 1884, the Imperial quicksilver works at Idria, Austria; in 1889, the New Almaden mines of California. But his great work was the creation of the school, of mining and metallurgy at the University of California, which may be said to have begun with his occupancy of a full professorship of these branches. It is not necessary here to recount the early difficulties and perils of the University, and its long struggle for academic independence of political control or interference. The battle is over, and the institution is now upheld by the intelligent loyalty of the citizens of California, without regard to party. But while the issue was uncertain, the development of special schools of applied science was scarcely practicable. Doctor Becker and William Ashburner had given up the school of mines as a hopeless task when Christy, younger and less experienced, took it up. As he wrote me in February, 1901-

Jan 4, 1915

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946