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By D. Turnbull, R. E. Cech

FISHER, Hollomon, and Turnbull have developed a theory for the nucleation of martensite. They first tested the theory on Fe-C alloys and low alloy steels. The major factor influencing nucleation of martensite was considered to be statistical composition fluctuations occurring in small regions at high temperature and frozen-in on quenching. These local regions of varying size and composition serve as nucleation centers. They become supercritical, one by one, as temperature is progressively lowered, resulting in temperature-dependent or athermal transformation. Fisher next applied nucleation theory to substi-tutional solid solution alloys. Detailed predictions were made for Fe-Ni alloys because of the availability of free energy data on this system. It was shown that composition fluctuations that were significant energy-wise did not occur, and nucleation frequencies could be calculated from average properties of the system. Nucleation was predicted to occur as time-dependent and having the functional relationship to give a C curve of nucleation frequency vs temperature. The analysis further predicted that the nucleation frequency was extremely sensitive to composition. Experimentally, it would be found that the transformation in some compositions is so slow that measurable amounts will not form in a reasonable length of time. With other compositions, only slightly different, the nucleation frequency becomes so great that the material becomes transformed while still distant in temperature from the maximum nucleation frequency. On quenching an alloy of such composition, the observed transformation kinetics would be similar to those found in Fe-C alloys. Cech and Hollomon repeated experiments of Kurdjumov n which the kinetics of transformation were similar to those predicted by Fisher for Fe-Ni alloys. The alloy studied in this investigation contained 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn. Fisher,' using an idealized model for the extent of transformation as a function of the number of martensite crystals per grain of parent phase, derived nucleation frequencies from the transformation curves of Cech and Hollomon. Complicating influences such as coupling effects between grains in the polycrystalline specimens were neglected. Nevertheless, excellent agreement was found between the theoretically and experimentally derived nucleation frequencies. These experiments, however, could not provide a critical test of the theory. Experimental nucleation frequencies could vary widely from those calculated, depending upon the extent of deviation from ideal partitioning and the extent of coupling effects. Further, since the compositions of material theoretically analyzed and experimentally determined were different, the free energy changes involved in the experimental work could only be estimated. Also, the effect of heterogeneities on the transformation kinetics was not considered. For these reasons, it was decided that experiments designed to test the validity of the Fisher analysis must be conducted on binary Fe-Ni alloys, which were the ones considered theoretically by Fisher. The martensite transformation in Fe-Ni alloys has been the subject of considerable study. Machlin and Cohen have shown that transformation proceeds in a manner quite unlike that in any other ferrous alloy system. They found that single crystals would transform to a large extent in a single burst. In large grain polycrystalline specimens, frequently more than one grain and sometimes the whole specimen would transform at the same instant in this manner. Results on filings indicated that different particles would undergo the burst transformation at widely different temperatures. These results support the conclusion that the transformation behavior could not be described by a single nucleation frequency as would be the case if the nucleation were homogeneous. It appeared that further work was necessary to define the factors responsible for burst-type transformation, so that the conditions could be altered to favor homogeneous nucleation of martensite if such could be accomplished. This report summarizes the results of some experiments conducted with powdered Fe-Ni alloys for this purpose and the re-

Jan 1, 1957

By Orville A. Derby

In view of the recent important discussions before this Institute on the genesis of metalliferous deposits, certain features in the occurrence of gold which seem to be more clearly developed in Brazil than elsewhere can hardly fail to be of interest. As the observations here recorded have necessarily been of a somewhat cursory character, they will be presented in the form of brief notes, without any attempt to draw conclusions as to their genetic significance. Gold in Gneiss.—The statement made by me many years ago† that in the districts of Campanha and S?o Gongalo, in southern Minas Geraes, gold occurs in gneiss, can now be reaffirmed in the most positive manner, on the strength of a recent examination of fresh material, confirmed by the testimony of an experienced mining captain from the Morro Velho mine, who, being skeptical on this point, made a prospectingtour in the district. The specimens examined, though so far decomposed as to be readily disaggregated, were clearly of

Jan 1, 1903

By B. M. Larsen

Jan 1, 1948

By B. M. Larsen

Jan 1, 1948

By George Rice

THE subject of dust explosions in coal mines first appears in the Transactions of this Institute following the first great mine disaster that happened in bituminous mines of the United States. This was the Pocahontas explosion, which occurred Mar. 13, 1884, causing the loss of 112 men. The operating company wisely asked the technical assistance of the Institute, requesting that a committee be appointed to investigate and report. This committee consisted of Messrs. Bramwell, Buck, and Williams, who, after careful study, reached the conclusion that the explosion was due "either to dust alone or to dust quickened by an admixture of fire-clamp too slight for detection by ordinary means." This is perhaps the first time in this country that coal dust was considered to be the chief agency in a mine explosion.. The report is given in the Transactions, vol. xiii, p. 237 (1885). It is particularly worthy of note that the committee called attention to "the necessity of full-sized tests and systematic experiments. " In the same volume of the Transactions, there is a most interesting paper reviewing the literature relating to coal dust, by E. S. Hutchinson, entitled Notes on Coal-Dust in Colliery Explosions. Mr. Hutchinson gives a historical account of observations on the part played by coal dust in mine explosions, beginning with Messrs. Lyell and Faraday's report on the Haswell colliery explosion in 1844, in which it is said "much coal gas had been made from this dust in the very air itself in the mine by the flame of the firedamp, which raised and swept it along, and much of the carbon of the dust remained unburned only from want of air." The subject lay dormant until 1875 when William Galloway began some coal-dust experiments in a small gallery at a mine in South Wales of which he was manager. At that time he considered the presence of firedamp necessary for continued propagation of a dust explosion; but in 1884, the year of the Pocahontas disaster, he stated that no earlier author-than himself had credited coal dust with being a principal factor in mine explosions, relegating firedamp to a secondary place.

Jan 10, 1914

By George J. Clark

One of the major problems of operation in the anthracite industry is the disposal and handling of refuse—not because of its complexity but because of the quantity and type of material involved. It is the purpose of this paper to describe the kinds of refuse, methods of disposal, quantities of material to be handled and equipment used, together with present day application at specific operations in the Northern, Eastern Middle, Western Middle and Southern anthracite fields. For the purpose of this paper, refuse is considered to be any material that has no present or foreseeable future value and that must be handled and disposed of in the process of mining and preparing anthracite for market. Included in this classification are tunnel rock, mine rock, cleaner plant refuse, breaker refuse, old timber, ashes and silt. Disposal Methods Old timber is disposed of either by burning or by depositing on the refuse bank. Burning is preferred because timber on the refuse bank is a potential fire hazard. Ashes are deposited on a separate bank, mixed with other refuse, or flushed into old mine workings. In many places, the latter practice has caused considerable difficulty in preparation of coal mined from these areas. In depositing ashes on the surface, it is wise to refrain from mixing them with material containing coal as such contamination may prevent reclamation of the coal in future years. Tunnel work, mine rock, cleaner plant and breaker refuse compose the bulk of the material to be disposed of and handled, and are referred to collectively as "refuse" in this paper. Waste material in or adjacent to the coal beds may be removed at the working face wherever possible. This can be done in flat or lightly pitching beds, and in the Northern field represents a sizable percentage of this type of refuse handled. In the other three coal fields, this method of disposal cannot often be used. Refuse not removed at the working face is taken to the surface and generally is deposited on banks; occasionally it is crushed and flushed into old mine workings. Breaker refuse often is used for constructing berms for silt-retention basins. Disposal Problems The problem of handling refuse is different for each operation, owing to topographical conditions, quantity of material to be handled, anticipated requirements and types of equipment in use elsewhere at the operation. Preparation plants with limited refuse-disposal areas, excessive grades to reach the required elevation and long hauls to disposal areas not readily accessible require the selection of equipment to best meet the conditions. The quantity of refuse to be handled from a given amount of raw material varies considerably throughout the four fields. In mine coal, this varies from a low

Jan 1, 1949

By AIME AIME

Council. * PRESIDENT OF THE COUNCIL. JAMES F. KEMP NEW YORK, N.Y. (Term expires February, 1913.) VICE-PRESIDENTS OF THE COUNCIL. S. B. CHRISTY BERKELEY, CAL. W. A. LATHROP PHILADELPHIA, PA. GARDNER F. WILLIAMS WASHINGTON, D. C. (Term expires February, 1913.) KARL EILERS NEW YORK, N. Y. WALDEMAR LINDGREN WASHINGTON, D. C. BENJAMIN B. THAYER NEW YORK, N. Y. (Term expires February, 1914.)

Mar 1, 1912

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-' cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

C. Edward Stafford, Chester, Pa.:—Doring all my business life, I have been engaged in the manufacture of Bessemer and open-hearth steels, but, during my long connection with the Shoenberger Steel Co. of Pittsburg, I had some experience in the manufacture of high-grade puddled iron for horseshoes, and in making, by Dr. Otto Wuth's process, extremely pure, low-phosphorus puddled blooms (analyzing from 0.005 to 0.01 per cent. of phosphorus and sulphur), which were melted with low-phosphorus pig-iron in acid open-hearth furnaces, to make extra locomotive fire-box steel. I have also seen the Danks puddlers in operation at different times and places, notably where they were most successful, at the Otis Steel Works, Cleveland, Ohio; then under the management of our friend, Mr. S. T. Wellman. These Danks blooms were made solely for open-hearth melting-stock, to which they were well adapted. (The unavoidable presence of bits of ore-fix imbedded in the mass of the metal always prevents the profitable manufacture of merchant iron from Danks' blooms.) With the experience just described, I was to some degree in position to value fairly the means, methods and results of Mr. Roe's mechanical puddling from the metallurgical or technical and economic points of view, when given an opportunity by Mr. Roe to see his puddling-furnace or machine in operation in Pottstown, Pa. Briefly, the furnace, with water-cooled bottom, is rectangular in plan, about 20 by 8 ft. in the clear, suspended by trunnions at the middle of the long sides, at a height of 17 or 18 ft. above the general level. The oscillation (65" each way from the vertical) is accomplished by geared segments (attached to the downward-projecting side or trunnion-plates) with which engage pinions driven by a reversing engine. The whole section

Jan 1, 1906

Jan 1, 1970

By K. G. Black, B. P. Faulkner

Laboratory batch flotation rests are used for comparison of the floatability of ores and for comparison of the effect of various treatments on ore floatability. Although it is difficult to predict exact recoveries for continuous flotation on the basis of batch tests, considerable quantitative information can be obtained through their use. A simple method is presented which provides a convenient means of quantitatively evaluating results from laboratory batch tests. The information obtained is in the form of a discrete flotation rate distribution, which, if desired, can be used directly in a simulation of continuous flotation. Equation of Batch Flotation The validity for batch flotation of the first-order kinetic equation is accepted: [ ] where k is flotation rate of a class of articles and W (t) is weight of particles of the class in cell at time t. Thus, at time t, the fraction of the original amount of the class of particles still remaining in the cell is [ ] where W (0) is weight of class of particles in cell at time zero. If there are several classes of particles in the cell, each with its own flotation rate, k4, the fraction of the particles remaining is [ ] where W (t) is now the total weight of n classes, a, being the original fraction of W (0) belonging to the ith class. Accordingly, [ ] [Fig. 1] shows the result of a typical batch test. Such result can be characterized by a set of particle classes, each set described by a flotation rate, [ki,] and a corresponding fractional magnitude, [ai.] [ ] Multiple Regression Equation Eqs. 3 and 4 may be combined to give

Jan 1, 1973

By S. G. Malghan, A. L. Mular

Size distribution and surface area measurements play an important role in the characterization of crushed and ground granular materials properties. This paper outlines sampling methods of granular materials followed by a detailed treatment of principles of size and surface area measurements of a wide range of sizes from crushers feed to ball-mill ground sub-micron particles. Currently available equipment for size distribution and surface area analysis is described and critically examined with respect to advantages, range of application and precautions in their use. Equipment for on- stream size analysis is also evaluated. Finally, a list of criteria are given for selection of particles size and surface area measuring devices for a particular application.

Jan 1, 1982

By J. K. Stanley, R. F. Meel

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By R. F. Meel, J. K. Stanley

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By B. B. Bucky

THIS investigation was carried on by means of models and the applica-tion of the principles of similitude to determine the effects of props, props and cribs and sand filling in longwall mining. The geologic structure and rate of face retreat were kept constant and the only change introduced was in the method of support. It is not felt necessary to repeat a description of apparatus, or to explain the fact that a scalar model made in all parts of the same material as the prototype will behave similarly to the prototype when rotated at speeds such that the centrifugal force is as many times the gravitational force as the prototype dimension is a similar linear model dimensions. The reader is referred to earlier papers1,2 for further information regarding these statements. All models were made of sandstone and were as in Fig. 6. They are composed of a 3/16-in. ore body bed A, overlain by a 3/16-in- bed B, a 3/8-in, bed C and two 1/8 -in. beds D and E. The model was rotated at ±2350 r.p.m. equivalent to a model ratio of 1268. It was worked back 1/4 in. at a time before being replaced in the centrifuge and again rotated. Table 1 gives model and prototype dimensions occurring in this discussion, the prototype dimensions being 1268 times the model dimensions. Figs. 1, 2, 3 and 4 were taken while the model was rotating at 2350 r.p.m. One was taken for each face retreat of 26.4 ft., but for obvious ,reasons all are not presented. Fig. 1 (A-E) shows the behavior of this type of structure with face retreats of 26.4 ft, and no artificial support. Fig. 2(A-E) shows the behavior of this type of structure where breaker and face props were used. The props were exceptionally strong, being of steel 1/8 in. square in cross section, and capped with 1/16 in. ± of soft wood and paper, to allow for roof deflection. The face props were

Jan 1, 1939

By Richard Maclin Stewart

A priest at Shenandoah, Pa., one day persuaded the president of the Philadelphia & Reading Coal & Iron Co. to slush breaker waste and culm into old mine workings in order to save his church from being destroyed by surface subsidence. The year was 1864, the project was successful, and history recorded the first use of hydraulic backfilling. Shortly afterward, the method was applied to several eastern coal mines for area fill to control subsidence. In 1884, hydraulic backfilling was used to control a mine fire in the Schuylkill region of Pennsylvania. The idea was taken to Europe by German engineers and developed successfully at the Myslovitz colliery in Upper Silesia in 1901. From there it was applied to several mines throughout Europe.

Jan 4, 1958

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 B. C. Craft

Development and exploratory work in Mississippi during 1934 was rather active, resulting in the expansion of the proven area and the drilling of a number of important wildcat wells. Mississippi showed a decrease in drilling operations during 1934. There were 36 completions from 18 counties during this period compared with 58 completions from 22 counties during 1933. There was a considerable decrease in activity in the Jackson gas field in Hinds and Rankin counties with only 9 completions, resulting in 8 gas wells and 1 dry hole compared with 17 gas wells, 2 oil wells and 7 dry holes during 1933. Leasing and geophysical work was reported from several sections of Mississippi last year. Extensive exploration and drilling were carried on in Lamar, Hancock, Pearl River, Greene and Stone counties and on the flanks of the Jackson anticline. Exploration will be continued in these areas during 1935. Four important wildcats were completed during 1934, all of which were reported as being structurally high, but without having important shows of oil or gas. These tests were: Hix and Germany's, J. J. Newman Lumber Co. No. 1, sec. 21-4N.-15W., Lamar County, abandoned at 3520 it. in the Wilcox; United Gas Public Service Company's Davis No. 1, sec. 30-1N.-5W., Greene County, abandoned at 7439 ft.; Gulf Refining Company's May L. Williams No. 1, sec. 33-5S.-17W., Pearl River County, abandoned at 4800 ft.; and Clarke County Oil Company's S. B. Kirkland No. 1, sec. 10-2 N.-16E., abandoned at 4002 ft. in the Eutaw. Another interesting wildcat was Gulf Refining Company's Dantzler Lumber Co. No. 6, sec. 22-4S.-llW., Stone County, abandoned at 7700 ft. (according to reports below the Selma chalk). A total of 114 of the 132 gas wells completed in the Jackson gas field are still producing and have a combined open-flow capacity of 4,145,-696,000 cu. ft. Four of the abandoned gas producers were never connected to the lines. The open-flow capacity of three wells in the Amory field is approximately 1,000,000 cu. ft. Producing against a line pressure of 50 lb., the demand during December greatly exceeded the capacity.

Jan 1, 1935

By R. F. Mehl, W. Batz, C. Wells

L. S. Darken—It is indeed gratifying to find that the results of the two different methods here reported are in substantial agreement with each other and with the earlier work1 of two of the authors. Dr. R. P. Smith, of our laboratory, has been conducting some experiments at 1000°C to determine the diffusivity of carbon in austenite by a third method— the steady state method. This work, which will soon be reported, is far enough advanced that we can say it is in substantial agreement with that of the present authors. The only disparity which might be considered significant is in the high-carbon region, where we find that the diffusivity rises a little less steeply than indicated in fig. 8. F. E. Harris—The authors have presented an impressive arrangement of data concerning the diffusion of carbon in austenite. Of particular interest is the compilation, table IV, which is repeated in col. B of table V for direct comparison with values (col. A. table V) from a formulation using a single Q value of 31,000 cal as the activation energy for diffusion. This comparatively simple formulation has been used quite successfully in the practical application of calculating the carbon added (or removed) through the face in carburizing and decarburizing experiments, where the face concentrations are held quite constant for known times and temperatures. Literally hundreds of tests have been so checked where the computed and experimental values have varied by less than 5 pct. For higher temperatures, where proper carburizing data are hard to obtain, the diffusion couple is treated as a decarburization of the high-concentration bar and as a carburization of the low-carbon member. The analysis has been limited to a maximum of 1.40 wt pct carbon. The agreement between cols. A and B in table V may be considered fair, if a liberal viewpoint is taken. The use of a diffusion couple has one serious drawback, in that comparatively small amounts of carbon pass through planes of concentration close to those of the initial high-carbon and low-carbon members, and hence small errors become important. In addition to the sensitivity at these high and low concentrations.

Jan 1, 1951