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By AIME AIME

THE meeting of the Petroleum Division at Houston, Oct. 10-12-headquarters, Rice Hotel-was preeminently a technological success. Two hundred and twenty-five attended the Thursday morning session and approximately 200 attended the sessions on Thursday and Friday afternoons and Saturday morning. Harry Power, Chairman of the Division, in his opening remarks, credited Paul Weaver and M. Albertson, respectively chairman and vice-chairman of the local committee, with working long and prodigiously in organizing the program. The theme of the initial session was indicated by Mr. Albertson in a statement relative to the estimation of developed petroleum reserves. He said that the problem of securing more accurate estimates of developed petroleum reserves existed prior to curtailment of production. With curtailment, however, the problem became an acute one. Mr. Albertson gave some of the more important reasons for this situation. Since the decline-curve method became inapplicable, the volumetric method has become the chief one used. It depends on the factors of productive formation volume, porosity, saturation, and recovery. He briefly discussed the factors necessary for application of the volumetric method. P. P. Gregory discussed the estimation of petroleum reserves in prorated lime¬stone fields (see his paper in the October

Jan 1, 1935

By D. W. Fuerstenau

This paper presents the results of an investigation of the stability of the mass flow rates and average pellet size in the different streams of an industrial-scale balling circuit. The variables in this study include water content, drum speed, and fresh feed rate. It was found that both the mass flow rates and pellet diameter are greatly disturbed when a change, positive or negative, in any of the variables takes place. For most of these disturbances to be damped down, a period of 1 hr or so is required. When a disturbance in the feed rate was made, the transient period extended to more than 1% hr (the duration of the experiment). It was observed that there is an interaction between the drum speed and moisture needed for producing an acceptable green ball product. The moisture content of the product pellets was found to be a function of the pellet size, with the larger pellets retaining a higher moisture content

Jan 1, 1983

By R. R. Templeton

THE year 1924 was particularly notable in the petroleum industry of California as it was a period in which extensive town-lot drilling, with attendant overproduction and allied problems, virtually ceased and the industry returned to a nearly normal condition. Nearly all major field operations were conducted by large operating and marketing companies; in contrast to 1922 and 1923 field operations, when small promotion companies set the pace and forced the large companies to follow. The outstanding features of petroleum development were: 1. The three major fields of 1923, namely Huntington Beach, Long Beach, and Santa Fe Springs, declined from a production of 13,042,939 bbl., in January, to 6,764,417 bbl., in December, a drop of nearly 52 per cent: During this period, Huntington Beach declined 35 per cent., Long Beach 42 per cent., and Santa Fe Springs 63 per cent. 2. Methods of pumping deep wells were improved in some particulars; this contributed toward sustaining the productions of these three famous fields above what was predicted. 3. Of the fields producing previous to 1924, only three increased in production to any appreciable degree, during the year, as the result of bringing in new wells. These fields are Dominguez, Torrance, and Wheeler Ridge. Dominguez, discovered in September, 1923, produced 56,851 bbl. in January and increased regularly to a production of 1,641,042 bbl. in December. Torrance increased from a production of 972,261 bbl. in January, to 1,783,670 bbl., in May, and then declined to 1,393,215 bbl. in December. Wheeler Ridge, discovered in January, 1923, produced 23,254 bbl., in January, 1924, increased to a high of 33,678 bbl., in September, and declined to 27,430 bbl. in December. 4. Nearly all the production that had been shut-in during 1923 was opened in 1924, except some wells chiefly in Coalinga, Fullerton, and Santa Maria districts. The opening up of this shut-in production, combined with the increased productions from Dominguez and Torrance, were the chief factors that held the rate of decline for the state to a gentle slope.

Jan 7, 1925

By J. Doig, A. A. Bauer, F. A. Rough

AN investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems was conducted by studying alloys ranging in composition from uranium-31.5 at. pct Mo to uranium-34 at. pct Ti. A ternary cut showing these phase relationships is presented upon the basis of thermal-analysis data obtained and upon the basis of metallographic and X-ray examination of heat-treated and quenched specimens. Isothermal ternary sections, inferred from phase relationships determined between the two 6 phases, are presented for the uranium-molybdenum-titanium system. In the compositional range investigated, a y-ura-nium solid solution exists at elevated temperatures. At about 900°C the 6-U2Ti phase, with limited molybdenum solubility, forms. Epsilon, a molybdenum-titanium-rich solid solution appears at the same temperature and appears in all phase regions that exist below this temperature except in the terminal 6-phase regions. The y phase is stable to approximately 660°C in titanium-rich alloys; the y and 6-U,Ti phases decompose at this temperature to a uranium in a peritectoid reaction. The y phase in molybdenum-rich alloys of the ternary cut studied decomposes in an apparent eutectoid reaction, at about 593°C, to the 6-uranium-molyb-denum and a-uranium phases. The e phase while present, presumably plays a negligible role in these reactions. Titanium was found to markedly decrease the stability of retained y in these alloys. Age-hardening characteristics developed in titanium-contain ing uranium-molybdenum alloys quenched from 900°C and aged at 500°C are ascribed to decomposition of Y to the a and E phases. INTRODUCTION Alloys of uranium with molybdenum, titanium, and zirconium, respectively, are of great interest because of their potential use as reactor fuels. As a result, this interest extends to the constitution of these alloys, particularly in view of their uniqueness of constitution. In these systems, alone, among known uranium-alloy systems, an intermediate phase forms by direct decomposition of the high-temperature y-uranium phase. As a prelude to possible future alloy development, an investigation has been undertaken of the phase relationships that occur between the intermediate phases of these systems. These phase relationships have already been reported for the intermediate 6 phases of the uranium-zirconium and uranium-titanium systems.' The results of an investigation of the phase relationships between the 6 phases of the uranium-molybdenum and uranium-titanium systems are reported here. The phase relationships that occur in the binary systems pertinent to this investigation are shown in Fig. 1. Phase nomenclature appearing throughout this report is as shown in these diagrams; the crystal structure of the phase is given in Table I. EXPERIMENTAL PROCEDURE Alloys were cast and fabricated to flat plate. Specimens were heat treated and examined metal-

Jan 1, 1959

By P. Shahinian, J. Weertman

Minimum creep rates of nickel samples were measured in the stress region of 2.5x107 to 2.8xl0 dyne per sq cm and the temperature region of 400° to 1100°C. The creep rate seems to be proportional to (stress) at stresses below 7x10H dyne per sq cm. The activation energy of creep is approximately 65,000 cal per mol. IN a recent theory' of steady-state creep which is based on Mott's dislocation climb mechanism, the following creep equation was derived for creep in polycrystalline metals (if where K is creep rate, Q the activation energy of self-diffusion, S the entropy of activation of self-diffusion, L' the grain size, L the subgrain size, b the length of the Burgers' vector of a dislocation, u the shear modulus, u the stress, a the critical shear stress, M the density of active Frank-Read sources, v the vibrational frequency of a vacancy, and kT has its usual meaning. This equation predicts a creep rate which depends on the stress through a power law at low stresses. At high stresses the creep rate increases much more rapidly with stress. The theory breaks down for stresses great enough that the inequality holds true. It was the purpose of the present in-

Jan 1, 1957

By John Chipman, Eric R. Jette, O. B. Ellis

IN the study of the chemical reactions occurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Herty1 and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schackmann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete analyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were remelted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abandoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the constituents of basic open-hearth slag. EXPERIMENTAL HEATS The first set of measurements on slagmetal equilibrium was made in the Research Laboratories of the American Rolling Mill Co. at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Research Laboratories at Massachusetts Institute of Technology, and will be referred to as series B. Series A.-The induction furnace used has been described.5 Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

By O. B. Ellis, Eric R. Jette, John Chipman

In the study of the chemical reactions orcurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Hertyl and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schack-mann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete allalyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were re-melted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abnndoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the con stituents of basic open-hearth slag. Experimental Heats The first set of measurements on slag-metal equilibrium was made in the Research Laboratories of the American Rolling Mill Co, at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Rescarch Laboratories at Massachusetts Institute of Techology, and will be referred to as series B. Series A.—The induction furnace used has been described. Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

By John Chipman, Eric R. Jette, O. B. Ellis

In the study of the chemical reactions orcurring in the open-hearth furnace, it is frequently assumed that a condition of equilibrium between slag and metal is attained. In order to test this assumption it is necessary to have dependable operating data as well as an exact knowledge of the equilibrium state. Considerable progress has already been made in the study of slag-metal equilibria, notably in the earlier work of Hertyl and of Oberhoffer and Schenck2 and in the more recent researches of Krings and Schack-mann3 and of Koerber and Oelsen.4 None of these investigators, however, have employed basic slags comparable to those encountered in basic open-hearth practice, so that up to the present time our only information regarding the equilibria of these slags is based upon observations drawn from steelmaking practice in which there is little assurance that actual equilibrium was attained. The original plan of this investigation was to secure simultaneous slag and metal samples at intervals during the making of an open-hearth heat, recording the heat history in detail and obtaining complete allalyses of slag and metal, then to bring these slag samples into equilibrium with liquid iron in the laboratory induction furnace and thus to determine directly whether or not the observed relationships in the open hearth represent conditions approaching equilibrium. This plan was only partly successful. While slags were obtained from the open hearth under satisfactorily recorded conditions and these were re-melted in the laboratory under equilibrium conditions, changes in slag composition, which accompanied the remelting operation, were so great that the final slag from the induction furnace bore little resemblance to its open-hearth parent and the direct comparison was therefore abnndoned. The results, however, lie within a range of slag composition that is of interest in the making of low-carbon steel. As far as we are aware, they represent the first published laboratory study of equilibria involving slags that contain all the con stituents of basic open-hearth slag. Experimental Heats The first set of measurements on slag-metal equilibrium was made in the Research Laboratories of the American Rolling Mill Co, at Middletown, Ohio. This will be known as series A. The second set was made in the Metallurgical Rescarch Laboratories at Massachusetts Institute of Techology, and will be referred to as series B. Series A.—The induction furnace used has been described. Approximately I kg. of a special ingot iron containing less than

Jan 1, 1941

By William Kent

ABOUT a year ago, the writer had occasion to assist Mr. John L. Gill, Jr., of the Pittsburgh. Car-wheel Works, in making a trial of his new testing machine. A piece of Bessemer steel, of about .34 carbon, was used as a test-piece, turned to a sectional area of one square inch for a length of five inches between shoulders, and pro¬vided with large round heads, which were fitted to what is called the " Wade grip." Measurements of elongation, accurate to , 1/10000 of an inch, were made by a special apparatus containing two micrometer screws, with electric contact attachment. The machine was operated by hand-power. Readings of elongation were taken at each increment of 2000 pounds stress per square inch, up to 44,000 pounds, the elongation corresponding to the latter figure being .0088 inch. The elongations up to this point remained almost exactly proportional to the stresses, the strain diagram, as shown on the Plate, from the origin to the point A, being a straight line (the deviation of no observation from the straight line being greater than .0002 inch). There being no indication of an approach to the elastic limit, the attendant at the hand-wheel and scale-beam was told to proceed as usual and move the poise forward 2000 pounds, or to 46,000, and turn the wheel until the beam was balanced. Noticing that the beam did not rise in the usual time, and that the elongation was increasing rapidly, the writer called to the attendant to stop turning the hand-wheel and to push the poise backwards until the scale-beam balanced. Instead of balancing at between 44,000 and 46,000 pounds, as was expected, it balanced at 40,000 pounds, and the elongation had increased to .0343 inch (or more than four times that recorded at 44,000 pounds), as plotted at the point B, the dotted line between A and B showing the supposed course of the strain diagram between these two points. Immediately upon recording the elongation the writer said to Mr. Gill, who was standing alongside: "This phenomena is without a parallel in my experience, and I know of but one way to account for it. The piece must actually be broken in its interior, through a flaw or weak portion of the metal. The test-piece is now equivalent to a tube, with

Jan 1, 1880

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By Roy C. Kirkman

Dear Editor: It is with great pleasure that I read Mr. Howard M. Wells article in the December 1978 issue of MINING ENGINEERING entitled: "Optimization of Mining Engineering Design in Mineral Valuation." Mr. Wells very adequately presents the case and point that there are a great number of variables which must be analyzed during an economic evaluation of an FUND RESOURCE, such as copper or uranium. I wish to take this opportunity to suggest that, given today's economic climate, decision making takes place under conditions of uncertainty and that this uncertainty justifies our need to examine each one of the parameters entered into the evaluation model. It is my contention that the influence of the tonnages and grades as well as their distributions, have the most profound effect upon the results of an evaluation. Everyone concerned with the evaluation of FUND RESOURCES realizes that as metal prices decline or stagnate with sharply rising direct operating costs, cutoff grades (Gc) must increase according to the equation below which Mr. Wells uses: Gc = Total Operating Cost/(Market Price X 20 X Recovery) However, historically, we have seen cutoffs move dramatically lower in both the copper and uranium industries for the past decade. Henceforth, this established the metals industry most important argument for processing greater tonnages of lower grade materials from disseminated deposits (refer to paper by Kirkman, Roy C.). These disseminated deposits, created by either concentration processes (uranium) or dispersion processes (copper, gold, molybdenum), have log-normal grade distributions (Fig 1). Gross profits are rising, but unit profits are falling. The industry has created longevity through economy of scale, i.e., mining vast tonnages of low grade. In order to develop the great tonnages necessary to prove economic viability, we must examine alternatives at the low-end of the tonnage grade relationship. Notice from [Fig. 2] that as we move further to the right away from line A-B drawn tangential to the average grade curve at 45°, total profits will increase (given fixed annual production capacity) and unit profits decrease. The theoretical optimum operating point is where: [ ] At this point my observation is that slight shifts in production capacity bring about greater changes in profitability due to greater grade changes. Therefore, the best financial risk evaluation is obtained by totally revising the mining engineers methods and fixing the financial parameters such as discount and interest rates. A 10% shift in either of these two parameters will not cause near the same variance in economic viability as will a change on the GRADE-TONNAGE curve [(Fig. 2)].

Jan 1, 1980

By F. G. Tryon

This paper treats only of the practicability of introducing a standard classification into the records of production and distribution of coal which we try to keep in the Bureau of Mines. From the point of view of gathering and analyzing statistics, the requirements of a satisfactory classification are that it shall be so definite as to eliminate the factor of arbitrary judgment, that it shall be reasonably simple and, finally, and most important, that it shall be understandable to the trade. In other words, to be woven in the statistical record it must be adapted to the raw material which flows in from the 7000-odd mines that produce the coal. The success of any scheme of classification, from the point of view of use, will depend largely on the degree to which it utilizes the accumulated experience of the trade and employs as far as may be possible the accepted trade designations. The experience of the Tidewater Coal Exchange during the war would be an excellent point of departure for a use classification of the coals of the Eastern Appalachians. Although the exchange long since passed out of existence, coal is still quoted and sold by the old pool numbers, and they have shown rather extraordinary vitality. Some years ago, in the Geological Survey, the experiment was tried of getting operators to classify their own coal by offering them a list of standard designations on the annual statistical questionnaire. The results were more amusing than informative. What with the confusion in terminology and the natural temptation to put one's best foot foremost, there was a general tendency to grade up the quality. Floods of semi-bituminous coal flowed in from many sources, millions of tons from districts where not a pound of that quality has ever been produced. The producers of semianthracite in Arkansas almost without exception would report their product as anthracite and their neighbors in the little Paris field, producing a fine blocky house coal averaging about 17 per cent, volatile, would say, "Our coal isn't anthracite; it's a semianthracite." Finally we discontinued the publication of those data as being more misleading than helpful.

Jan 1, 1930

J. E. JOHNSON, JR., New York, N. Y. (communication to the Secretary*).-The discussion of Mr. Henrich's paper took place at a meeting from which I had the misfortune to be absent, and has just come to my attention. I do not wish to let the subject pass without contributing to it a little information which has come into my possession. In 1912, I published a brief note in the Transactions on The Effect of Alumina in Blast-Furnace Slags, giving in tabular form three typical slags used in iron blast-furnace practice, one of them the high alumina slag of, which Professor Richards speaks. That table is reproduced herewith. TABLE 1.-Composition of Slays. 1 3 3 4 5 6 7 CaO by Neutral Ratio Ratio Ratio Al2z03, SiO2, Differ- Substan- Cat Ca0 a A1203 Ratio Per Per ence, ces, CaO Cent. Cent. Per Per Al2O3 + Sioz Sit: SiO2 Cecil_ Cent. Virginia practice 6.5 36.0 54.0 3.5 1.27 1.6S 1.50 Lake-ore practice 13.5 33.0 50.0 3.5 1.08 1.92 1.51 Special experiment... 36.0 24.7 36.8 3.5 0.59 2.90 1.44 It supplies what seems to me convincing evidence that, for the purposes of the iron blast furnace, alumina can be regarded only as a neutral substance, dissolving in the slag and materially altering its viscosity, but not affecting its chemical activity. In subsequent experience with charcoal furnaces, I found the same rule to hold; that the chemical effect of alumina could be disregarded, providing the ratio of the lime and magnesia to the silica were kept constant. This is exactly the experience which Messrs. Dwight and Mathewson had in copper- and' lead-smelting furnaces. I have never seen any evidence or argument adequate to support the contention of Professor Richards-that the alumina acted as a base in the charcoal iron furnace and as an acid in the coke furnace, and that the function of alumina in iron-furnace slags is inherently different from that in copper- and lead-furnace slags-and I am compelled to differ absolutely with his conclusions in that respect.

Jan 9, 1917

By W. R. Purcell, C. S. Brooks

The internal surfaces of rocks which are in contact with interstitial fluids are known to influence in some degree the recovery of hydrocarbons from pay zones. Despite the admitted importance of the influence of solid surfaces on hydrocarbon recovery, little information is available concerning the extent of surface of reservoir rocks. In this paper a description is given of the apparatus and procedure employed in the determination of the surface areas of sedimentary rocks, and values are reported for a variety of sandstone and limestone cores. In addition, consideration is given to the Kozeny equation, which relates surface area to porosity and permeability. A colliparison is made between the surface areas as calculated from this equation and the geometrical areas of a series of packs of spherical glass beads. Also, for a group of sandstone cores. Kozeny areas are compared with surface areas as determined by the gas adsorption method employed in this investigation. INTRODUCTION It has long been recognized that many processes which are of importance to hydrocarbon production are controlled in some degree by the extent of the surface of the reservoir rock through which the hydrocarbons move. For example, the recovery efficiency that is obtained in a given reservoir is certainly determined in part by the action of interfacial forces between the reservoir fluids and rock, and this action is influenced in turn by the extent of solid surface. Despite the admitted importance of surface effects to problems of petroleum recovery, little information is available concerning the extent of surface of reservoir rocks." It is the purpose of this paper to describe an apparatus which has been employed for the measurement of the surface areas of rock samples and to present the values which have been obtained for a variety of sandstone and limestone cores. In addition, the relationship of surface area to permeability and porosity, as given by the Kozeny equation, will be discussed. METHOD OF MEASURING SURFACE AREA The method of determining surface areas as employed in this work has previously found wide use in studies of porous solids such as catalysts. The method involves the measurement of the amount of physical adsorption of an inert gas, such as nitrogen or argon, on the bare surface of the solid at reduced pressure and constant temperature near the normal liquefaction temperature of the gas. With the aid of the theory of isothermal adsorption as developed by Brunauer, Emmett, and Teller,' it is possible to ascertain the amount of gas (and hence the number of molecules) which is required to cover the solid surface with a single layer of molecules. From a knowledge of the covering area per molecule the total surface ares of the solid can be computed. Since the Brunauer. Emmett, Teller (BET) theory has been adequately discussed elsewhere: it will suffice here merely to present their final equation as ordinarily employed for surface-area calculations. This equation relates the volume of gas, V, which is adsorbed at pressure, P, to the liquefaction pressure, Po, of the gas, and to the volume of gas, V.,, that is required to form a monomolecular layer: In this equation C is a quantity which is related to the heats of adsorption and liquefaction of the gas; for a particular solid-gas system at Constant temperature, C is considered to have a constant value. The basic adsorption data can be presented in the form of Equation (1) by plotting the quantity P/V(Po- P) as a func-

Jan 1, 1952

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By R. A. Bergier

The Transactions of the Institute contain nothing, as yet, on the subject of pocket-compasses; and in the belief that American miners, explorers, geologists, and engineers will gladly welcome any infor mation about new forms of apparatus, simple in construction and adapted to rapid use, I offer a short description of an improved French combination pocket-compass, which, if once introduced into use, would seem likely to supersede similar instrumens of older pattern. The instrument in my possession I owe to the kindness of M. G. de.La Bouglise, of Paris. The frame of the compass is a double-bottomed box, 2 1/2 inches square and 9/16 of an inch high, made of white metal, and with its sur faces very carefully planed. The sides of the box make true right angles with each other. Two sides are parallel with, and two are normal to, the north and south line of the principal graduation. The bottom is accurately planed, so that the instrument will lie true on a plane surface. A glass, 2 3/8 inches in diameter, is set in the top plate. The graduation for the needle is engraved on the upper face of a ring, connected with the flat disk, in which the center-pin is in serted. Between this disk and the bottom of the box there is a hollow space a quarter of an inch deep. The needle is 1 7/8 inches in length, and can be balanced by means of a small sliding piece of metal. The graduation extends from 0° to 360°, reading from right to left. The stopping of the needle is effected by a screw, A, on the side of the box near the handle, H (Fig. 1). There is also a clinometer attachment, the graduation for which is engraved on the upper face of the silver-plated disk. The compass has two sights. The north sight, B, is a simple pin, a little more than an inch high, which, when not in use, is kept folded down, and is partially protected by the exterior sliding-plate, C. When raised for use, the sight is stopped in a vertical position by a projecting pin attached to the side of the box.. The south sight, D, is connected with the handle, H, and the sight and handle

Jan 1, 1890

By William Hutton Blauvelt

Coke is the product of dry distillation of bituminous coal, by which the volatile matter is driven off, producing a hard body of cellular structure. Not all bituminous coals will coke, and there has been much discussion regarding the substance which is present in coking-coals to distinguish them from dry coals. Professor Lewes says that the bituminous matter in coal is largely derived from the spores of fossil mosses. Resins are present in all soft coals, and contribute largely to the cementing of the coke. The resinates and hydrocarbons begin to distil out at moderate temperatures and leave the pitchy residual, which at 500' C. forms a mass already well caked together, if the proportion of humus residual is not too great. This coke is soft, but if the heat be raised to 1,000° C. the pitch decomposes further, leaving carbon, and Professor Lewes is convinced that the coking bond is due to these liquid products which distil off, leaving pitch, which then carbonizes and binds the mass into coke. Professor Parr concludes that the structures of the organic compouilds of the coal Which furnish the cemeding-material for coke, and which are apparently attacked by oxygen, have not been determined and seen] to vary somesvhat in different types of coal. However, they yield, on oxidation, humic acids of varying composition which decompose into powdery residues. Because of the complex nature of these substances and the difficulty experienced in isolating and identifying them, the theory of coking is still an open problem and the explanations advanced are largely hypothetical. In the coking process the volatile matter driven off in the oven consists mainly of tar, ammonia, and gas, familiarly known as by-products. Both the quality and quantity of coke and by-products vary greatly With the composition of the coal.

Jan 1, 1913

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

IN a previous article' the authors outlined a study of the variables in rod milling and also reported data from a series of open circuit grinding tests on a massive limestone in a 30-in. x 4-ft end peripheral discharge rod mill. As a second part of the experimental program, an analysis is now presented for the 30-in. x 4-ft overflow rod mill grinding under identical conditions, except that discharge ports on the periphery of the mill shell have been sealed so that the products from the present series overflowed through a 9-in. diam .opening in the center of the end plate. A variance analysis has been made of the combined data for the two experiments, and performances of the two mills are compared here. Included in the first report' were descriptions of feed preparation, rod mill circuit, instrumentation and controls, and techniques used to evaluate data. Dependent and independent variables were defined, and variance analyses were made to test the relative significance of variables and to establish magnitude of error for the experiment. Significant data were plotted in various combinations, and conclusions were drawn from the graphs. The procedure and analysis in this series of tests follows the first tests and is not repeated. Data from the second series are recorded in Table I. Listed in the first three columns are the independent variables of feed rate (1000, 2000, 3000, 4000, and 5000 1b per hr), mill speed (50, 60, 70, 80, and 90 pct of critical), and pulp density (50, 60, 70, and 80 pct). The dependent variables, Pso, P100, reduction ratio, slope of the log-log sieve analysis curve, power demand, and Bond work index follow. Of these, only the reduction ratio and the Bond work index were analyzed for significance. Production of new surface as calculated from sieve analyses has not been included for this series because of the questionable assumptions that have to be made to satisfy the formulas involved. The large number of products obtained during the runs precluded the use of surface measurement techniques by the gas adsorption methods at this time; however, samples of all products have been stored for future reference. To test the consistency of the reporting of the sieved products, an averaged sieve analysis was calculated from the wet-dry plots obtained from the three product samples of each run. The resulting averaged analysis was plotted and the P80, selected. The relative deviations of the P80's from each of the three product samples with respect to the P80 of the averaged analysis were then calculated. In only two sets were the relative deviations (6.2 and 9.9 pct) considered excessive. In each of these two sets, one sieve analysis was obviously out of line; hence that analysis was ignored and new averages were computed. This reduced the relative deviations to 1.2 and 2.7 pct respectively. The relative deviations of the product analyses with respect to their averages ranged from 0.1 to 1.4 pct at 1000 lb per hr, 0.0 to 1.1 pct at 2000 lb per hr, 0.2 to 3.0 pct at 3000 lb per hr, 0.3 to 4.3 pct at 4000 lb per hr, and 0.5 to 5.2 pct at 5000 lb per hr. The relative deviation of the 80 pct passing point for 96 dry sieve analyses of the feed with respect to that of the averaged analysis was 7.6 pct. This slightly higher percentage can probably be attributed to a greater proportion of tramp oversize in a crusher product than is ordinarily found in a rod mill product. The last column on Table I lists the adjusted work index, which has been used as the measure of efficiency for the various combinations of operating conditions investigated. Efficiency increases as the index becomes lower. It was reported in the previous paper that the work indexes for the Waukesha limestone used in these experiments decreased as the product size decreased (as calculated from Bond grindabilities). That is, this limestone becomes easier to grind as the material becomes finer. This is unusual, because the work index for most materials as calculated from the Bond grindability has remained constant as the product size decreased or has increased slightly. Table II lists the results of Bond grindability tests at all mesh sizes from 3 to 200 and the work indexes calculated from them. To remove this variation of work index with product size from the data so that results would apply to any material of constant work index, the work index values shown in Table II were plotted against product size on log-log paper. From this curve (a straight line function in this case), the expected work index for the product size for each of the runs of the experiment was obtained. The work indexes as calculated from the reduction ratio and energy consumption were then divided by the corresponding expected work index. The results obtained are reported in percentages on Table I as adjusted work index and are actually percentages of the work index for the Waukesha limestone at the size in question. Multiplication of the work index value for a material of constant index by these percentages should allow the application of the adjusted work index curves to the material. Only the adjusted work index values, not the actual experimental values, were used for the variance analyses and for the graphs.

Jan 1, 1956

By E. P. Dahlberg, R. E. Reed-Hill

On the assumption that stress or strain relaxation occurs as the result of a thermally activated process, equations are derived relating to tensile experiments that give the strain as a function of the time under the condition of constant stress, and the stress as a function of the time for constant strain. It is demonstrated that if the strain-rate equation i = previously proPosed by Kuhlmann., is used as a starting point, then the relaxation of strain at constant stress may be expressed by the equation c = (-RT/(Y) 1tz tanh (t + is the strain capable of being relaxed at any given instant. Similarly, it is shown that the relaxation of stress at constant strain may be given by a = (-RT/B) In tanh (t + t0)/27, where a is the instantaneois value of the relaxable stress. The fact that these relationships reduce to well-known empirical equations at both large and small values of the stress Or strain is also shozcn. The present theory is shown to agree well with experimental data obtained from tensile elastic aftereffect experiments on a zirconium specimen prestrained at 77 k as to make it strongly anelastic. It is also demonstrated that elastic aftereffect data obtained using torsional specimens ?,Lay agree reasonably well with the equation derived for the case of tension. RELAXATION experiments are often employed as a means of studying metallic deformation mechanisms.' The simplest and most commonly employed techniques involve stress relaxation at constant strain and strain relaxation at constant stress. In general, however, investigations of this nature have been seriously handicapped in the past by a lack of suitable equations giving the time dependence of the relaxing variable over an interval that extends from small strains up into the region where internal-friction experiments become strain-amplitude dependent. This paper presents a derivation of such a set of equations for the case where the time-dependent part of the strain is anelastic or recoverable and the specimens are loaded in simple tension. The relaxation of strain under the condition of constant stress will be considered first. Let us assume that strain relaxation occurs as the result of a reversible thermally activated process that occurs at a number of relaxation centers lying in an elastic matrix. Then, following Kuhlmann,2 we may express the rate of strain relaxation as follows: where C is the strain rate, AFx the free energy of activation of the process controlling strain relaxation, a, the effective or average resolved stress at the relaxation centers, u an activation volume, R the universal gas constant, T the absolute temperature, > a factor with dimensions of a volume that accounts for the strain contribution of a successful operation of a unit process, N the number of relaxation centers per unit volume, and v the Debye frequency. The first term on the right of Eq. [I] represents a strain rate in the direction favored by the stress, while the second term represents the rate in the opposite direction. It is implied in Eq. [I.] that both F and v are symmetrical with respect to the two basic directions of operation of a relaxation process. Eq. [I] may also be written where and S and Q are the activation entropy and activation energy, respectively, of the relaxation process. In the following, A will be considered a constant. This is compatible with a set of experimental conditions where the relaxation rate is controlled by a single basic reversible process in which it may be assumed that the temperature dependence of the product ?Nv is negligible in comparison with the temperature variation of the exponential term. It is also implied that v, 7, and N do not depend strongly on a, . In deriving a relationship for the strain as a function of the time from her equation, equivalent to Eq. [2], Kuhlmann2 chose to consider only the limiting cases where the time was either very small or very large. It will now be shown that it is possible to integrate Eq. [2] to obtain a single equation valid over a wide range of strains if the concept of relaxable strain is introduced. The use of this quantity, which is the difference between the instantaneous value of the strain and the value of the strain at complete relaxation, represents the primary point of departure of the present theory from that of earlier workers. Let us express the effective stress at the relaxation centers in terms of strain. For this purpose we may use the following equation derived by zener3 for the case of strain relaxation at slip bands: where M? and M are the relaxed and unrelaxed moduli respectively, go the applied constant tensile stress, and m an average orientation factor that takes account of the fact that a,, the effective stress at the relaxation center, may not be a tensile stress (i.e., a

Jan 1, 1967