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By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By W. L. Freyberger

In a study of the kinetics of flotation of coal, employing a single-cell continuous flotation system, Jowett and Safvi1 pointed out that it was experimentally impossible to float all of the coal which could be floated in a batch tests. On the other hand, deBruyn and Modi, in a discussion of their paper, suggested that under certain conditions the recovery of floatable material from a similar one-cell continuous system would have been 100%.2 Both of these pairs of authors make the assumption that a state of perfect mixing exist in the flotation cell. This assumption, usually made by investigators studying flotation kinetics in a continuous system, has been confirmed experimentally on several occasions. The work is summarized by Arbiter and Harris.3 It is the purpose of this note to demonstrate that, for conditions of perfect mixing, one of two conditions exist: 1) the recovery of floatable material is 100%, and the flotation is infinitely fast, or 2) the recovery of floatable material must be less than 100%. This theorem can be proved simply in the following manner: 1) If recovery, R, of the floatable material is 100%, the concentration in the tailing must be zero. This follows from the definition of recovery as

Jan 1, 1964

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940's the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual' published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By R. W. Balluffi, B. H. Alexander

RELATIVE diffusion rates of copper and zinc in a brass have been measured in a vapor-solid type of couple with which the amounts of copper and zinc diffusing past inert Kirkendall markers can be obtained by means of a few simple experimental measurements. If inert markers are placed on the surface of copper which is then exposed to zinc vapor from a brass chips, the particles become buried due to outward diffusion of the copper, as shown in Fig. 1. A schematic diagram of such a couple after diffusion is shown in Fig. 2. Consideration of the diffusion flow of copper and zinc shows that the entire hatched area, including the cross-hatched area, is proportional to the amount of zinc diffused inward past the markers and that the smaller cross-hatched area is proportional to the amount of copper diffused outward past the markers. These areas are completely determined by the expansion of the couple, the depth of the buried particles below the surface, and the chemical composition at the specimen surface. As Darken1 has shown, the ratio of diffusivities of copper and zinc is then given by the ratio of these two areas. Polycrystalline copper and two copper single-crystals made by the Bridgman method were prepared in the form of 1.5 cm diam disks approximately 0.5 cm thick with faces plane and parallel. Tungsten particles approximately 0.001 cm in diam were bonded to the surface of each disk by heating 5 hr at 1060°C in vacuo. Each specimen was next

Jan 1, 1953

By K. P. Anderko

INVESTIGATIONS of the constitution of the system Mg-Ba were first made by Grube and Dietrich1 between 0 and 47 atomic pct Ba and then by Klemm and Dincke1acker" ver the whole composition range. Klemm and Dinckelacker corroborated intermediate phases of the approximate formulas Mg9Ba and Mg4Ba, and showed a third compound to have the formula Mg2Ba, rather than Mg5Ba, as suggested by Grube and Dietrich. Mg2Ba had been previously recognized by Hellner and Laves3 s a MgZn2 (C14) type structure. The main discrepancies between the results of Grube and Dietrich and those of Klemm and Dinckelacker exist, however, in the liquidus temperatures and solidification equilibria of alloys containing more than about 10 atomic pct Ba. The liquidus temperatures measured by Grube and Dietrich, and the outline of the liquidus of Klemm and Dinckelacker are plotted in Fig. 1 on an enlarged scale. Although there are strong reasons to prefer the results of Klemm and Dinckelacker, it was considered worthwhile to remeasure liquidus temperatures of some alloys in the controversial composition range. The alloys, made up from sublimed magnesium and 99.5 wt pct pure barium, were melted in an Armco-iron crucible in a dynamic argon atmosphere. Thermal analyses were taken using a Speedomax auto- matic recorder. Careful stirring during the solidification process was required in order to avoid segregation. After thermal analysis some of the cast alloys were chemically analyzed. The intended and analyzed compositions of the ten alloys prepared are listed in Table I. Since standard barium determinations cannot differentiate between barium present as element and as oxide, both the barium and magnesium contents of the alloys were analyzed. The fact that the sum of barium and magnesium was close to 100 pct in each case was taken as evidence that no excessive oxidation had occurred. The liquidus temperatures measured are listed in Table I and plotted in Fig. 1. As can be seen, they are in good agreement with the liquidus found by Klemm and Dinckelacker. This leaves no doubt that the thermal results of Grube and Dietrich above 10 atomic pct Ba are incorrect. This work was performed under the sponsorship of the Pitman-Dunn Laboratories of Frankford Arsenal, Philadelphia, Contract No. DA-11-022-ORD-1975. Sponsorship and permission to publish by this organization are gratefully acknowledged.

Jan 1, 1958

By H. C. Vacher, C. J. Newton

EXTENSIVE investigations in the field of residual strain measurement by X-ray diffraction have been made by Bollenrath, Hauk, and Osswald,1 by Smith and Wood,2'3 by Greenough; by Rosenthal and Norton." and many others. Since X-ray strain measuremeits apply only to those crystals of the test body which are of the proper condition and orientation to diffract and since the residual strains revealed may be accompanied by either body or tex-tural stresses, there has been considerable disagreement among investigators with respect to the validity of conclusions in this field. Although the experi-mentors have employed a variety of loading schemes, surface preparations, and X-ray wave lengths, the observations almost invariably have been made only on the outer surfaces of the specimens. The present note is not to be construed as an exposition of a new method of stress analysis by X-ray strain measurements on sections but as a presentation of some results which point to interesting possibilities for further experiments with sections. The two test rods used in this study were of ingot iron annealed at 910°C. The initial length of the gage section was 2 in. and the diameter was 0.415 in. Cross-sections were cut from the ends of the annealed rods to provide strain-free material. The tensile rod was axially loaded the desired amount in a commercial testing machine. A 1 in. portion of the gage length was cut from the other rod and was subjected to compression in the same machine. Details of this plastic straining of each rod are given in the upper half of Table I. A half-cylinder piece about 1/4 in. long was obtained by making a short longitudinal plane cut containing the axis of the rod near the center of the gage length. From adjacent material a disk about 1/8 in. thick was cut to provide the cross-section specimen. Later another section was cut from this same region with an angle of 30" between the normal to its surface and the axis of the test rod. A cross-section and a longitudinal section were cut from the compression rod in a similar manner. All of these as well as the strain-free cross-sections were mounted in Bakelite and used as specimens for the following X-ray strain measurements. During the course of the study, it became apparent that the condition of the surface of a specimen was a highly critical factor. One of the annealed strain-free specimens as a control was subjected to about 24 hr of polishing with fine alumina, interrupted about every 2 hr for etching with 1 pct nital. Its lattice parameter was determined at intervals from measurements on back-reflection X-ray diffraction patterns, which were calibrated with diffraction from tungsten powder. The parameter gradually approached the value found in the literature for strain-free iron and remained there, within the limits of the experimental error. This determined a long polishing and etching procedure which was adopted for all the specimens and which gave X-ray results from the surfaces believed to be representative of each specimen as a whole. A large number of back-reflection patterns were made with cobalt and chromium radiation, all at normal incidence. Except for some preliminary stationary exposures made to monitor the removal of cold work from the surfaces, each exposure was made with the specimen slowly translating and the film slowly rotating. In appropriate cases a thin layer of a standard metal powder, tungsten with cobalt radiation and silver with chromium, was dusted over a film of vaseline on the surface of the specimen to serve to calibrate the X-ray patterns. After the preliminary work, four films were made,

Jan 1, 1956

By B. L. Averba

THE determination of retained austenite by X-ray diffraction uses the following relationship:"" Pa = constant . RVaA (8) [1] where: P is the diffracted power from phase a; R, the calculated intensity factor; A, the absorption correction; 8, the diffraction angle; and Va, the irradiated volume of phase a For a flat sample making a glancing angle + with the incident beam the absorption correction is calculated as: * 1 sin (28 - 4) A .= 1 [2] µ sin, (28 — 4) + sin 4 where µ is the linear absorption coefficient. Beu3 has proposed that the computed absorption correction be combined with the constant and that the experimental observation of the absorption correction used in the original method be eliminated. This procedure is permissible only if: 1—There is no preferred orientation in the sample, and 2—The geometric requirements have been met precisely. If these conditions are not met the validity of the determination is questionable. Unfortunately the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2. In practice it may be convenient to plot P/R vs the parameter sin (2? — )[sin (28 — +) + sin +] to obtain straight lines for the ap- parent absorption correction. Deviations from straight lines indicate either that the sample has not been positioned correctly or that the relative intensities are incorrect. Geiger counter spectrometer methods also have been used successfully for retained austenite determinations. In the usual spectrometer arrangement the sample makes equal angles with the incident and diffracted beams (8 = ); thus the absorption correction is simply 1/2µ and independent of 8. The retained austenite is then easily calculated from integrated intensity measurements on austenite and martensite lines. If the austenite content is not too low and if excessive fluorescence is not encountered it is possible to use filtered radiation and a recording spectrometer. The integrated intensities are then proportional to the areas of the diffraction peaks. For lower austenite contents the following technique was used: A bent quartz monochromator and a Geiger counter spectrometer are employed. The monochromatic radiation is focused on the front slit, and the counter slit is made broad enough to include the entire line. A series of readings are taken in the vicinity of the diffraction peak. The highest reading includes the diffraction line plus background. The background is obtained from the average of several readings on each side of the peak. The integrated intensity is obtained by subtraction. CrK, and FeKa have been used for such determinations. This technique has been found to be as sensitive and as accurate as the photographic methods. In the spectrometer methods the ratio austenite/ martensite may be obtained from readings on austenite and martensite lines and the application of Eq. 1. It is also possible to use external standards and to obtain the austenite contents from measurements on the austenite lines alone. The small correction for carbides then becomes unnecessary. The best standards are probably samples with known

Jan 1, 1954

By Lawrence Adler

MINE hoist ropes have hitherto been selected by successive approximation, a process both tedious and inexact. The proposed expression is a readily solved synthesis of existing data and the following standard equation:' [ W + Wr + (W + Wr) -a 9 (W + W)f + b] n=T [1] For convenience, a glossary of all terms appears on page 564. Since rope weight (W,) and bending load (B) are functions of unit rope weight (Wv), which in turn is a function of rope strength (T), W, and B can be expressed in terms of T. W, as a Function of T: A study of the curve in Fig. 1, unit rope weight vs strength, yields Eq. 2: W. = -f- [2] Therefore Wr = WvL = T. [3] iv B as a Function of T: From Fig. 2, unit rope weight vs diameter, Eq. 4 is obtained: W, = 1.6d2 [4] B is related2 to d and D, and d has been expressed in terms of W, by Eq. 4, so the curve B vs W, (Fig. 3) gives Eq. 5: 177,000 177,000 This may readily be checked from the expression3 for a 6x19 rope, i.e., d3 B = 288,000D Since d2 = 0.625 W, and N = substituting d into the above expression gives Ea. 6: 180,000 180,000 B T, which will be used. [6] Into Eq. 1 substitute Eq. 3 and Eq. 6, noting that f=0.02: W + T 1.02+=T. [7]

Jan 1, 1958

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.' Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.' The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans' calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

By G. W. Tracy

The material balance equation has been used for many years by engineers to determine reservoir performance. The use of this equation in general has been twofold: first, to determine the oil-in-place in a reservoir; and second, to predict the future performance. The Schilthuis form of the material balance equation, or one equivalent to it, has been used by many of the engineers. The use of the Schilthuis form in predicting future performance has proved to be laborious in that one generally must make several estimates at each step of the trial and error calculation before arriving at a check of the oil-in-place. A method is presented for expediting the calculations. The Schilthuis form of the material balance has been rearranged into a more useable form. In using the material balance to predict the future performance of a reservoir, it has become common practice to estimate the incremental oil production for each step of the calculation which corresponds to a given pressure reduction. Instead of estimating the incremental oil production, the method outlined in this paper better lends itself to estimating the instantaneous gas-oil ratio. A check of oil-in-place is more easily accomplished by estimating gas-oil ratio since it is less sensitive to small inaccuracies. This method incorporates the same self-checking feature inherent in the Schilthius form. DEVELOPMENT OF SIMPLIFlED EQUATION In the development of the simplified equation, the Schilthuis form of the material balance equation will he used. Substituting in Equation 1 for and rearranging terms In Equation 2, the cumulative oil production (n) is multiplied by a factor which is uniquely a function of pressure. Also, the cumulative gas production (G) and net water influx are also multiplied by factors which are a function of pressure alone. These factors are called and are defined as follows: Using these factors, Equation 2 becomes The equation in this form is easier to manipulate mathematically than any of the previous forms which, have been used. Sources of data for the pressure factors are a bottom-hole fluid analysis and the ratio of initial gas cap volume to oil volume in the reservoir. AID IN DETERMlNING THE ORIGINAL OIL-IN-PLACE Each of the curves and +, have a similar shape. Each is infinite at the bubble point pressure. As lhe pressure is reduced below the bubble point, the

Jan 1, 1956

By D. W. Fuerstenau

In 1940 Schuhmann1 showed that the size distribution of a comminuted material can be expressed by the following empirical relationship: y = 100 (|f [i] where y is the cumulative percentage of material finer than size x, k is a size modulus, and a is a distribution modulus which is constant for a given material and machine. During the past few years, considerable emphasis has been given to the investigation of the extent of size reduction resulting from the expenditure of mechanical energy in crushing and grinding. Recently Schuhmann' presented a derivation of the energy-size reduction relationship by postulating that comminution in a device such as a ball mill can be considered to be the summation of many single comminution events, each of which yields a size distribution of particles following the Schuhmann size distribution equation. By grinding

Jan 1, 1961

By C. W. Chen

MARTENSITE transformations in ß Cu-Al alloys have been studied by Greninger1 and other investigators. According to Greninger, the parent phase ß1 an ordered body-centered-cubic structure obtained from ß phase by suppressing the eutectoid decomposition, transforms into an ordered hexagonal-close-packed phase in composition containing 12.9 to 14.7 pct Al. The M, temperature decreases with increasing aluminum content; for the alloy containing 14.5 pct Al, for example, the ß1??' transformation occurs below room temperature. More recently, Kurjumow2 studied the transformation in ß Cu-Al alloys with the addition of nickel. His report stimulated new interest in the subject due to the observation of completely reversible transformation without hysteresis in the transformation temperature ranging from 10° to —10°C. In the present paper some characteristics are described of the transformation of Cu-Al-Ni alloys that were partly studied by Kurjumow. Experimental Procedure High purity copper (99.999 pct) and aluminum (99.99 pct) and electrolytic nickel were used in the preparation, by the Bridgman technique, of single crystal specimens which contained aluminum and nickel of 14.5 and 0.5 to 3.0 pct, respectively. Polished surfaces were prepared mechanically. Specimens were then chemically etched to remove distorted material, homogenized at 1000°C for several hours, and quenched drastically to room temperature in a 10 pct NaOH bath to produce the parent phase ß1. The transformation was studied under a microscope and, in some cases, recorded by means of motion pictures. A device similar to that designed by Greninger and Mooradian3 was used to cool and reheat the specimens. Results and Discussion When the specimens were cooled below room temperature, the ß1 to ?' transformation began at 10°C with the appearance of ?' crystals In relief, Fig. la. As the specimen temperature dropped further, the transformation continued, either by the growth of the ?' crystals, with the ß1 — ?' interface moving into the ß1 phase, Fig. 1c and 1d, or by the formation of new ?' crystals, Fig. 1b. As a consequence of the former process, banded structure is observed as a common feature of the low temperature phase. According to the theory of the formation of martensite by Wechsler, Lieberman, and Read,' the bands of ?' phase are probably twin-related, as is the case in the diffusionless phase change of In-T1 alloys,5 but this was not revealed by X-ray tech- niques. New ?' crystals, in needle form, often emerged suddenly across the ?' bands during the transformation. These acicular crystals then grew, both in length and in width, see Fig. 2a through 2d. The transformation on cooling is completed at about -35°C. Upon heating, the reverse transformation started at —10° C, in a manner nearly opposite to the transformation on cooling, and completed at 35°C. There was no noticeable change in the transformation temperature when the nickel content was varied within the limits previously mentioned. Through control of the specimen temperature, the transformation can be started, stopped, or reversed at will. This phenomenon has frequently been observed in the martensite transformation of many nonferrous alloy systems. Other systems are Au-Cd6 and In-Tl.5 ow-- ever, in the latter systems, the transformation is accomplished by single interface motion if the specimen composition is homogeneous and the temperature gradient in the specimen is uniform and sharp, whereas in the Cu-Al-Ni specimens, only multiple interface transformation is observed. The speed of the interface motion appears to be a functionof the rate of temperature change and the temperature gradient across the specimen length. In one case, in which the temperature increased at the rate of 10°C per min and there was no temperature gradient along the specimen axis, the speed of the disappearance of a ?' plate was determined, by the study of the motion pictures made, to be 26 µ per sec. Quench markings were observed on the polished surfaces of specimens. The markings were grouped into one or more sets of different orientations, and were parallel in each set. The ?' plates formed in subsequent transformation were parallel to the markings, indicating that the ?' plates and the quench markings had the same geometric relation-ship to the ß1 matrix. The quench markings on two intersecting surfaces of a specimen were therefore used in the determination of the habit plane of transformation, by the trace method suggested by Barrett.' Results obtained from five sets of markings in three specimens indicate that the habit plane is an irrational plane about 2" from one of the {221} planes. This is very close to the habit plane (3" from 221 planes) of ß Cu-Al alloys containing more than 13.0 pct Al.1 The martensite transformation of Cu-Al-Ni alloys is reproducible. No sluggishness was found between consecutive transformation cycles, although a slight difference in the distribution pattern of the ?' plates was observed, compare Figs. Id and 2d. The transformation can be strain-induced. This characteristic has been tested by a simple method. When a specimen was elastically strained slowly in a vise, ?' plates were gradually produced in the same fashion as during transformation on cooling, This test was done at room temperature, and thus above the M,

Jan 1, 1958

By L. D. Jaffe, D. C. Buffum

EARLY papers1-' reported that temper brittleness is influenced by microstructure. This conclusion was based on room temperature impact tests, the inadequacy of which has been pointed out. Pellini and Queneau7 measured impact energy absorption at —80O to +25oC for several microstructures. On the basis of the shift, associated with temper brittleness, in the energy vs testing temperature curve they concluded that tempered martensite is somewhat more susceptible to temper brittleness than is tempered pearlite. The range of temperatures was insufficient to give complete curves covering the transition from tough to brittle behavior, so it is difficult to evaluate quantitatively the shift for the different microstructures. Also, the smaller shift of pearlite might be attributed to its already being temper embrittled at its temperature of formation. Accordingly, blanks 2 3/16 in. long were cut from a heat of SAE 3140 hot rolled steel barstock, 5/8 in. diameter, on which other work has been reported? A set of blanks was austenitized 1 hr at 900°c, water-quenched, tempered 16 hr at 675oC, and water-quenched, giving a microstructure of 100 pct

Jan 1, 1954

By D. Turnbull, A. M. Turkalo

It is well known that if copper that has been severely cold-worked by rolling (70-98 pct) is heated to high temperatures a small number of large grains are formed at the expense of the fine grained structure that appears upon primary recrystallization. Dahl and Pawlek,' Cook and Mac-Quarie,2 Ward,3 and Boas and Bowles4 have studied this phenomenon in copper. It has been reported as taking place with measurable velocities in the temperature range 700-1080". Boas and Bowles have reported that the time necessary for the transformation is of the order of days at 700°C. According to Ward3 the number of secondary grains which appear in OFHC copper decrease with increasing perfection of cubical alignment after primary recrystallization; also the perfection of cubical alignment increases with decreasing grain size prior to the final reduction. In this investigation two heats, A and B, of especially high purity copper (99.999 pct) supplied by the American Smelting and Refining Co., were used. The behavior of samples prepared from the two heats was qualitatively very similar providing that the grain sizes established prior to the final reduction were about the same. We observed that in specimens prepared from bars which were relatively coarse grained prior to final reduction secondary recrystallization took place at a rapid rate at temperatures as low as 500°C. This is about 200-300°C lower than the temperature necessary to obtain fairly rapid transformation in OFHC copper. A 0.22 in. thick rectangular bar of lot B was cold-reduced 60 pct by straight rolling and given a penultimate annealing treatment at 250°C. Following this it was cold-reduced 90 pct and heated to various temperatures in the range 450-1040°C. The specimens were about 8 mils thick

Jan 1, 1950

By E. C. Roberts

TO facilitate some recent microscopic investigations it was necessary to devise special mounting techniques for the polishing of two quite different metallographic specimens. These techniques are extremely simple and are submitted for whatever value they may be to other investigators. The first specimen mount proved very satisfactory for the study of untempered martensite. Since it was undesirable to heat the specimen, lucite or bakelite mounting materials could not be used in the conventional manner. A cold mount was made by drilling a hole of the same diameter as the specimen in a cylindrical piece of polystyrene then press- ing the steel specimen into the hole on an ordinary vise. A prefabricated disk of lucite should work equally well. The only precautions necessary are that the hole be drilled out cleanly and the piece of steel be pressed into the plastic uniformly, otherwise the mount will crack. The second type of mount was required for the study of slag specimens by reflected light. Mounting these specimens in bakelite and then attempting to rough finish the surfaces on graded emery papers resulted in a considerable amount of chipping and breaking out of the slag particles. This made further satisfactory polishing almost impossible. It was found, however, that if the bakelite-mounted specimen was first rough finished to a point where a good specimen surface became visible, the interstices in the specimen surface could be filled and the polishing completed. This filling was accomplished by placing a small amount of lucite powder in the bottom of the steel specimen mold then reinserting the bakelite-mounted specimen on top of the lucite powder. Reheating the mold to the proper temperature and applying the required pressure resulted in the formation of a thin disk of lucite on the bottom of the bakelite specimen. By carefully grinding the lucite away a uniform surface including the slag specimen was obtained and further polishing was unhampered by slag disintegration.

Jan 1, 1951

By P. R. Hines

Diphenyl guanidine is used as an accelerator in vulcanizing rubber. Other rubber accelerators are also flotation collectors, e.g., dithiocarbamate, thiazole, and the xanthates. Urea and its derivatives are good flotation collectors,' and guanidine is the nitrogen analog of urea. These two characteristics suggested testing diphenyl guanidine as a flotation collector. Diphenyl guanidine has been tried in flotation work previously, but references give no details.'.' Bunker Hill Co. of Kellogg, Idaho, supplied the ore sample used in these tests. The sample was typical of the ore milled in 1949 and contained 4.52 pct Pb and 1.08 pct Zn. A flotation test made by the author with potassium ethyl xanthate as a collector, the same flotation reagents, and the same grind employed in regular Bunker Hill mill practice was the standard for comparing results with the compounds and derivatives of guanidine. The compounds and derivatives of guanidine are only fair collectors of galena. However, if potassium ethyl xanthate were used in the galena float, its presence later in the sphalerite float would make it impossible to introduce another type of collector and be certain which collector contributed the result, so the compound or derivative of guanidine under test was used in both the galena and sphalerite floats in Table I. On both the galena and the sphalerite in the Bunker Hill ore, the depressing action of sodium cyanide and zinc sulfate is much greater with collectors of the guanidine type than with the xanthates. If the depressing agents are left out when a guanidine type of collector is used, but a pH of 8.6 is maintained with either lime or sodium carbonate, the depressing action is approximately the same as in the standard xanthate test. Consequently the depressing agents, sodium cyanide and zinc, were not used in the galena floats of tests 1226, 1228, and 1286, Table I, so the galena floats would be on a comparable basis with the standard xanthate test. As shown by the tests in Table I, the loss in the tail when diphenyl guanidine is used is 8.3 to 9.3 pct, as compared to 17.6 pct with potassium ethyl xanthate, or a recovery of 2.3 to 2.0 lb more zinc. Concentrate grade is 13.7 pct with potassium ethyl xanthate and increases to 22.9 and 31.8 pct with diphenyl guanidine, showing a much higher selectivity. Unless the Barrett's No. 4 coal tar creosote is considered to be a collector, no collector other than diphenyl guanidine is present in the tests, Nos. 1226, 1228, and 1286. Tests 1218, 1253, and 1263 in Table I1 were run to check the effect of the depressing agents used in flotation of the galena (sodium cyanide and zinc sulfate) upon subsequent flotation of sphalerite by diphenyl guanidine. Urea was substituted for potassium ethyl xanthate in tests 1253 and 1263 because it is a good collector for galena and a poor one for sphalerite, and the effect of the depressing agents is more marked with urea than with potassium ethyl xanthate. Test 1205 checks the effect of urea alone without any depressing agents when used for the flotation of galena. Table I1 shows that diphenyl guanidine as a collector for sphalerite is compatible with other flotation reagents used in floating galena. When the depressing agents sodium cyanide and zinc sulfate are used in the galena flotation step, the amount of lime in the sphalerite flotation must be increased (compare 1253 and 1263). Table I11 gives some of the compounds of guanidine which were tested and compared. Some of the compounds and derivatives of guanidine* are solu- * Diphenyl guanidine is in commercial production and is available on the market. ble in water and others are not. Those tested were fed dry. When an organic collector is promising, its compounds and derivatives should be tested and their comparative collecting power recorded. Eventually, in this way, it may be possible to discover some of the essential chemical characteristics of a good collector. For example, it is interesting to compare the diphenyl and dibutyl derivatives in Table IV with those of urea in Table 111, Example 3, U. S. Patent 2,664,198. All are good collectors. Table I shows some of the effects of lime on recovery of sphalerite by diphenyl guanidine. Table V

Jan 1, 1960

By W. B. Lilienthal

A considerable saving in time and money has been effected by use of a specially designed stainless steel container for laboratory drilling mud test work. This container involves use of a standard tall-form stainless steel beaker for service in which the mud sample is heated to an elevated temperature and maintained there for protracted periods of time, while undergoing agitation to facilitate mixing of mud components. Agitation is accomplished by rotating the filled containers on motor-driven rollers within an oven. Several porcelain balls are generally placed in the containers to further improve agitation. Soft glass containers (.Mason jars) were used in this service in early work, and were found to be unsuitable for the following reasons: 1. Poor resistance to thermal shock. 2. Containers could withstand only relatively low pressures. 3. Accidental breakage in handling. 4. Chemical deterioration and subsequent mud contamination from reaction of high pH muds with the glass at elevated temperatures. Pyrex containers were also considered, but, inasmuch as they provided improvement only in items 1 and 4 listed above the additional cost was not believed to be justified. A scale drawing of the container is shown in the figure illustrating details in cross-section. A pressed stainless steel lid was fabricated to match the rolled edge of the beaker

Jan 1, 1950

By E. P. Klier, Volker Weiss, George Sachs

IT has been shown that the isothermal transformation of austenite in a special steel can be modified by isothermal holding in the high subcritical transformation range.' Since this treatment potentially leads to increased hardenability, limited testing has been completed to determine if the stabilization effects observed with this treatment can be used to advantage in the heat-treating of 4340 steel. As an index of the effects of the several austenitizing treatments on the hardenability of the steel, Jominy-type hardenability tests were completed for specimens 2.5 in. in diameter and 8 in. long. Since the steel studied is to be used at strength levels where notch sensitivity is of major concern, notch sensitivity after selected austenitizing treatments has been evaluated by notch tensile tests for several specimen sizes. The steel composition and the austenitizing treatments are given in Table I. The test specimens are presented in Fig. 1. The hardenability data are given in Fig. 2 and the notch tensile properties are presented in Fig. 3. The hardenability of the steel investigated when determined by use of the standard Jominy test specimen2 as high and remained essentially unchanged for the different austenitizing treatments. For the larger test specimen, as has been shown by other investigations," the characteristic hardenability indexes are changed and it becomes possible to isolate austenitizing treatments which promote maximum hardenability. The stepped austenitizing treatment promotes higher hardenability as is indicated in Fig. 2. The evaluation of notch sensitivity for very high strength steels is best accomplished by means of the notch tensile test. The experimental conditions of the test, however, modify the notch strengths measured, and in the present experimentation an effort was made to achieve a limiting notch condition by fixing the notch root radius at 0.001 in. while the specimen diameter was allowed to increase from 0.3 to 1.1 in.* For this root radius the notch strength, 0.3-in.-diam specimen, and this trend differs from that for the larger specimens. At the highest tempering temperatures the 1.1-ip.-diam specimens yield comparable results for the austenitizing treatments compared. However, as the tempering temperature is progressively lowered below 800°F, em-

Jan 1, 1958