Search Documents

By Glenn R. Zellars, J. P. Morris

The carrier gas method was used to measure the vapor pressure of copper over liquid copper and Fe-Cu alloys. From these results, the activity of copper in the alloys was determined at 146°, 1550°, and 1600°C. Calculations of the activity of iron were made from the results for copper. The activities of copper and iron show strong positive deviations from Raoult's law. KNOWLEDGE of vapor pressures of liquid metals has both practical and theoretical value. Fuming of metal baths is directly related to vapor pressure, and the data should bc particularly important to the technology of vacuum metallurgy. Theoretical applications include determinations of heats of vaporization, heats of solution, and activity coefficients in alloys. Methods for measuring vapor pressures of metals have been reviewed by Speiser and Spretnak.' High-vacuum procedures, such as the Langmuir and Knudsen methods, have been used most widely in recent years. However, these methods are not applicable to vapor pressures greater than lo-' mm Hg and often cannot be used in the temperature range of greatest interest. The purpose of this investigation was to develop a procedure for measuring vapor pressures of pure metals and alloys that would be applicable to pressures greater than lo-' mm Hg. The transportation or carrier gas method has been used. Copper was chosen for the initial work because its vapor pressure has been established fairly well and the reliability of the technique could be ascertained. Applicability to alloys was studied by determining the vapor pressure of copper over liquid Fe-Cu alloys. Experimental Procedure The tests were carried out in a graphite-spiral resistance furnace. The charge consisted of 50 g of metal contajned in a covered sintered-alumina crucible 1/2 in. deep and 13/8 in. ID. Two sintered-alumina tubes led from outside the furnace to within the crucible, passing through close-fitting holes in the crucible cover and radiation shield. The arrangement of the crucible and the two alumina tubes is shown in Fig. 1. The small-bore tube (1/16 in. ID by 5/16 in. OD) served as the inlet for the carrier gas. The tip of this tube touched the metal surface and the flow of gas imparted a rippling motion to the metal. In this manner the gas was brought into close contact with the metal and became saturated with metal vapor. In most of the tests the flow rate of the carrier gas was 560 ml per min, measured at room temperature. Approximately half of this saturated gas was allowed to escape from the crucible through the second alumina tube (3/16 in. ID by 5/16 in. OD) and was discharged to the atmosphere through a

Jan 1, 1957

By P. Greenfield, C. C. Smith, A. M. Taylor

J. E. Harris (Berkeley Nucclear Laboratories, England)—Greenfield et al.11 attribute abrupt changes in slope of their log o/log i curves for heat-treated Mg/0.5 pet Zr alloy (zA) to &apos;atmosphere&apos; locking. It is proposed here that a more reasonable explanation of the apparent strengthening at low rates of strain can be based on precipitation either during the preanneal or during the creep tests. All the tests were carried out above 0.5 Tm where solute atmospheres are likely to be largely evaporated2 and can migrate sufficiently rapidly so as not to impose any &apos;drag&apos; on the moving dislocations. McLean3 has derived an expression for determining the temperature Tc above which, due to the high-migration rate of the atmospheres, Cottrell or Suzuki locking can play no part in determining creep strength. This expression, which holds for an applied shear stress of not greater than 5 X 107 dynes per sq cm is: Tc/Tm= 7/6.8 - log10? where i = secondary creep rate The values for T, corresponding to the maximum and minimum reported creep rates at each temperature have been calculated from the data of Greenfield et al. These are given in Table VII. All the test temperatures were above T,, the margin being greater for the higher temperatures and for the lower strain rates where the breaks in the log s/log ? curves occurred. Dorn and his collaborators14, 17 have studied systematically the effect of solute hardening on the creep properties of an A1/3.2 at. pet Mg alloy. In the temperature range where strain aging occurred in tensile tests, abnormally high-activation energies for secondary creep were obtained but at temperatures above 0.43 Tm, solute alloying did not have any effect on the creep parameters. Moreover, there have been no reports of any strain aging phenomenon during elevated temperature tensile tests with ZA material.18 Instead of the observed strengthening being due to atmosphere locking, it is now proposed that precipitates play an important role in enhancing the creep strength of the material. There are two possibilities—precipitation of zirconium hydride during the high-temperature preanneal and/or precipitation of the hydride or a-zirconium during creep. On the basis of the former the results can be interpreted in terms of a critical stress being necessary to force the dislocations through or over preexisting precipitates. From the latter, if the strengthening is due to pre- cipitation during the test then hardening should be associated with a critical strain rate. At low rates of strain, time is available during the tests for precipitation to occur either directly onto dislocations (thus pinning them) or generally throughout the matrix (which would impede dislocation movements). Examination of the data of Greenfield et al. suggests that both mechanisms may be operative since they observed precipitation during creep and also found that their alloys exhibited high-creep strength in the early stages of the low-stress tests, i.e., before creep-induced precipitation had time to occur. It is not easy to understand why they considered that precipitation of zirconium hydride is unlikely to occur at 600°C while it can take place in tests in air at as low a temperature as 200°C. Precipitation of the hydride during the preanneal cannot be ruled out merely on the basis of metallographic examination. Hydride precipitates in ZA type alloys are very small and can only be accurately resolved in the electron microscope.9 For example, in this laboratory20 hydride platelets with major dimensions <(1/10) µ have been observed by electron transmission through thin film specimens of hy-drogenated ZA material. Complex interactions between dislocations and such particles are illustrated in Fig. 12. Additional evidence for precipitation during pre-annealing is provided by the data presented in Greenfield&apos;s Fig. 1 and Table IT. These show that the creep strength at 200o and 400°C increases with the time of preanneal at 600°C. Such increases cannot be explained on the basis of increases in grain size alone for further improvements in strength were observed when the material was annealed for longer times than that required to stabilize the grains. Although the main discussion is confined to ZA material, similar arguments can be used against the strain aging hypothesis proposed to explain the binary Mg/Mn alloy data. In this case no precipitation is possible during the preanneal, but precipitation-hardening during creep can occur.

Jan 1, 1962

By F. R. Morral, K. T. Aust

The preferred orientation and earing characteristics of ZS aluminum were studied. An empirical correlation was obtained relating earing behavior and variation of mechanical properties for face-centered cubic metals. Strain-ratio mecsurements for ZS were found to be in good agreement with Hill&apos;s theory of plastic anisotropy. DIRECTIONALITY in sheet metals may be revealed by earing in a cupping test, or by the variation of mechanical properties of tensile specimens taken at different angles to the rolling direction. However, no simple correlation appears to exist between earing and variation in mechanical properties in metals and alloys studied.1-5 Aluminum of commercial purity (known as 2S, with a specified minimum of 99.0 pct Al) cast by the direct casting process was chosen in the present investigation since ears at 45° or 0°, 90° can readily be obtained. Preferred orientation is often the principal cause of uneven metal flow, such as earing, and variation in mechanical properties. Consequently, the preferred orientation characteristics of 2s aluminum were initially studied using both X-ray diffraction and micrographic techniques. The variation of mechanical properties with angle to the rolling direction was next determined in an effort to clarify the apparent lack of correlation of earing behavior with mechanical properties for face-centered cubic metals. Strain-ratio*5,8 measurements were finally conducted to determine first, if the maximum values of the strain ratio occurred at the earing positions, and second, if Hill&apos;s theory of plastic anisotropy7 is applicable to other face-centered cubic metals such as aluminum. Detailed treatments, working, and heat treating are not given in this paper since this study is not concerned with the methods to produce earing, but to correlate earing with other properties and characteristics of the material. The percentage of earing was measured using the formula specified by the x—Y Aluminum Association, -------- X 100 = pct earing, where x is the height of the ear and y is the height of the valley from the bottom of the cup. Preferred Orientation Characteristics of 2S X-ray Studies: Beck and coworkers8 have determined that the rolling texture of 2s after 95 pct cold reduction may be approximately described by four equivalent ideal orientations near (123) [121]. Also, the recrystallization or annealing texture of 2s aluminum consists of four components of the (123) [l21] type, retained from the rolling texture, and of a (100) [001] or cube texture component." Fig. 1 illustrates the typical appearance of deep drawn earing cups with the corresponding X-ray diffraction patterns. The X-ray patterns were taken with copper radiation using the structure-integrating method&apos;" in which the specimen is scanned during the X-ray exposure. The rolling direction was vertical and the rolling plane was perpendicular to the horizontal X-ray beam. It was found that an increase in the retained rolling texture component resulted in a greater 45" ear height, while an increase in the recrystallization texture component (i.e., cube texture) caused greater 0°, 90° earing. X-ray diffraction studies of 2s cold rolled to final thickness followed by a final anneal have shown that the rolling texture, and also the retained component of the rolling texture after annealing, are increased with greater cold-rolling reduction. The preferred orientation characteristics of 2s sheets given an intermediate anneal between cold rolling followed by a final anneal were found to depend on the position of the intermediate anneal during cold rolling. For instance, three identical samples of 2s homogenized ingot, each 1 in. thick, were given the following cold-rolling and annealing treatments: 1—50 pct reduction, intermediate anneal, 96 pct reduction to 0.020 in. and a final anneal; 2—75 pct reduction, intermediate anneal, 92 pct reduction to 0.020 in. and a final anneal; and 3—90 pct reduction, intermediate anneal, 80 pct reduction to 0.020 in. and a final anneal. The intermediate and final annealing treatments consisted of a 70°F per hr heating rate, held 6 hr at 800°F and air cooled. Typical X-ray patterns after each of these treatments are shown in Fig. 2. It was evident that after treatment 1, the retained rolling texture component predominated; after treatment 2, the retained roll-

Jan 1, 1954

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.&apos;&apos; The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15&apos;16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author&apos;s Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener&apos;s equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By A. L. Bailey, B. A. Landry

All who are even generally aware of the tremendous rate of increase in coal washing operations must realize the growing importance of the float-and-sink test. I believe it is conservative to estimate that, in the past decade, the dollar volume of float-and-sink testing has increased tenfold. It is a simple matter of economy, then, to examine the factors that determine the cost of adequate float-and-sink testing. When the Coal Preparation Section of the Bureau of Mines entered upon a greatly expanded program of such work in connection with the synthetic liquid fuels investigations, it seemed advisable to examine these factors experimentally. The principal consideration that differentiates float-and-sink test sampling from general purpose sampling, is that the original particle size must be preserved. Therefore, the total cost of the test will be directly affected by any standard that might be proposed to limit sample bulk reduction at any given particle size. For this reason, the relationship of sample size to variability of results was the first factor to be studied experimentally. Of course, the matter is rendered complex by the circumstance that the float-and-sink test, not a simple analytical measurement but a process test, comprehends a number of more-or-less independent items of fundamental data; and as shown in the report, the&apos; variability of the samples differs with respect to these different items. This condition and the wide variety of situations in which float-and-sink test data are used, in combination with other factors, to study complex process operations, indicate the difficulty of setting up fixed standards for float-and-sink sampling and testing. At this stage at least, it is the intent rather to obtain experimental data on the principal Factors involved so that the reader may arrive more intelligently at a procedure adapted to his problem. The authors of this paper have presented experimental data showing the relationship between size of sample and particle size for different variability tolerances with respect to percentage of sink. In further studies, data are being collected to appraise also the variability of the samples with respect to float-ash content and size consist. The scope of this work will be broadened to cover particle sizes up to 4 in., and a third series of tests has yielded similar data for a much cleaner type of raw coal. Thus, the further studies will make available a fairly comprehensive meas- ure of variability with respect to size consist, percentage of sink, percentage of middlings, and percentage of ash in the float, for three coals ranging from 3.87 to 17.68 pct in refuse content (heavy sink material) and from 4.18 to 17.52 pct in middlings. Introduction At present there are no published standards for float-and-sink test sampling. During the rapid expansion of float-and-sink test work, varying procedures have been based on adaptations of the ASTM standards for sampling coal for analyses. For this reason, a special study of gross sample reduction has been undertaken to determine the limits for this step in the operation where no reduction in particle size is to be made before testing. Float-and-sink tests are made whenever a thorough study of coal characteristics is desired. The tests may be made on samples from coal-cleaning units such as jigs or tables, or coal samples may be tested which are taken from a loading boom, railroad car, or the coal seam itself. The resultant gross sample may be large and pose a problem of sample reduction. The question is, then, how much can the sample be reduced and still fall within preassigned limits of accuracy of the original gross sample of coal? Coal from channel samples may be crushed to liberate impurities and then separated into various gravity fractions from which washability curves are drawn; from these curves, it is possible to determine the cleaning characteristics of the coal. However, coal samples from coal-cleaning units cannot be

Jan 1, 1950

By D. R. Mash

A strong yield point with attendant enhanced mechanical properties was found in commercially pure beryllium under certain conditions of heat treatment. Beryllium specimens also responded to both quench and strain aging treatments. Based on these results, a possible means of obtaining increased normal temperature mechanical properties is suggested. COMMERCIALLY pure beryllium has been found to exhibit the yield point phenomenon and several other aging manifestations under certain conditions of heat treatment. This behavior is not surprising in view of the present accumulation of experience regarding such effects in numerous metals; but in addition to extending this experience to include beryllium, the present study is of interest because aging effects are generally associated with the presence of small amounts of solute elements. The well known lack of tensile ductility in beryllium at normal temperatures is also considered to be due to impurities in some way. In the present investigation, the view was taken that beryllium of commercial purity (greater than 98 pct) should be considered as a dilute alloy and that precipitation phenomena may well exist which could lead to enhanced mechanical properties. In connection with this possibility, published data on the variation of mechanical properties with temperature are of interest. For example, Fig. 1 illustrates the variation of ductility (percentage of elongation) and ultimate strength as a function of temperature for beryllium of various histories.* Although these curves are somewhat schematic in nature, they clearly indicate the possibility that precipitation of an unstable phase and/or aging effects occur during tests in the region 400" to 700°C. The existence of such behavior should be recognized as affecting the properties of the commercial material and perhaps can be employed advantageously. Experimental Method All testing was done at room temperature using a Baldwin universal testing machine. A microformer extensometer was used in conjunction with a micro-former-type stress-strain recorder. All tests were conducted at constant loading rate, the slowest rates being used. This corresponded to 120 lb per min in the 1200 lb full scale range and 300 lb per min in the 6000 lb full scale range. After the rate of loading was set in the elastic range of the material during the early part of the test, no further adjustments were made, allowing the test to proceed at that setting. In the plastic region of the curve above the yield region, strain rates of from 0.002 to 0.006 in. per min were regularly obtained. All experimentation was carried out on specimens machined from the same lot of beryllium, lot No. Y5036BP. Table I shows the chemical analysis as furnished by the supplier, Brush Beryllium Co., as well as the standard specifications to which commercial beryllium is produced. Both 1/4 in. thick hot pressed plate and ½ in. round hot pressed and warm extruded rods were obtained. The history of the material is reported to be as follows: 1—Beryllium metal plates, produced from a standard hot pressed QMV beryllium metal block 4x15x40 in., were cut off and finished machined to 1/4x6x12 in. flat plates. The original hot pressed block was made by hot pressing —200 mesh vacuum cast attri-tioned powder at about 1050°C under vacuum. 2—Beryllium rod was hot pressed and warm extruded. Extrusion billets were machined from the regular hot pressed blocks followed by extrusion at 425°C. The extrusion was done without jacketing, and graphite was used as a lubricant. The rods were then straightened at 720 °C, after which they were annealed at 800°C for 15 min. Both flat tensile specimens and round tensile specimens were tested. The former were machined from the plate stock into standard specimens according to specifications shown in ASTM E8-52T. The nominal cross-section was 0.25x0.500 in. and the gage length was 2 in. The round specimens were

Jan 1, 1956

By J. Lohrenz, R. J. Francis, G. C. Clark

Compositional material balance methods have been extended to solution gas-gas cap-water drive reservoirs. Partial or complete pressure maintenance as well as reservoir repressuring by gas and/or water injection may be considered. Increrments of reservoir withdrawals and injections equivalent to a given time increment are used as the basic iterative step to allow the extension. An example field study shows how the reservoir volumes. extent of the water drive, and relative permeability ratio function may be estimated. Knowing these, the methods can be used to predict reservoir behavior. INTRODUCTION The compositional material balance is similar to conventional material balances in many aspects. The assumption of a pressure-homogenous reservoir with no transients is common to all conventional material balances1-1 although numerical methods are different. The compositional material balance also contains this assumption. Inclusion of phase equilibria directly in reservoir calculations is the key difference and improvement in the compositional material balance. A continuous account of the compositions of the reservoir fluids and effluents is determined. Calculations of fluid phases and properties can be based on these compositions. Excepting fluid phases and properties determined in this manner, the compositional material balance uses procedures exactly analogous to conventional methods. Brinkman and Weinaug5 and Jacoby and Berry6 have given compositional material balances for simple solution gas drive reservoirs; subsequently Jacoby and Berry&apos; extended their procedure to include pressure maintenance by gas injection at constant reservoir pressure. This paper extends compositional material balance techniques to a more general combination drive reservoir with various types of pressure maintenance operations. The procedure for this extended compositional material balance and an example of its field application are presented. PROCEDURE The numerical calculations of this compositional mate- rial balance are performed on a high-speed digital computer. The most comprehensive case the present compositional material balance program can handle is a solution gas-gas cap-water drive reservoir with (1) water production, (2) water influx, (3) separate or commingled production from the oil and gas zones, (4) any surface processing arrangement including LPG and gasoline production, and (5) gas injection into the gas and/or oil zones." This description of the procedure applies to this most comprehensive case. Appropriate deletions in the procedure can be made for more simple mechanisms. ASSUMPTIONS In common with conventional material balances, the compositional material balance makes the following assumptions: (1) the total reservoir is at a uniform pressure at a given time; (2) the volumetric ratio of gas to liquid withdrawal at reservoir conditions is directly proportional to their mobilities; and (3) instead of assuming a pressure-dependent total gas-oil equilibrium, the cornpbsitional material balance makes a sianificantly different and more rigorous assumption as follows. Thermodynamic equilibrium exists for each component in the liquid-gas mixtures in the reservoir and in surface processing. These three assumptions are fundamental in the compositional material balance procedure. Other assumptions involve arbitrary simplifications of the reservoir mechanisms. This compositional material balance uses the following simplifying assumptions: (1) no bulk mixing occurs between the gas and oil zone; (2) total mixing occurs between any injected gas and the contents of the injection zone; (3) no in situ hydrocarbon liquid is produced from the gas zone; (4) no reservoir gas is retained behind any net bottom-water influx; (5) the residual saturation of hydrocarbon liquid at reservoir conditions behind any net bottom-water influx is constant; and (6) fluids retained behind any net bottom-water influx exert no further influence on the reservoir. These six assumptions are not fundamental. Modifications of the present procedure can be made for different assumptions of the reservoir mechanisms. THE TIME INCREMENT Previous compositional material balances have used a pressure increment for simple solution gas drive reservoirs"" and an increment of injected gas for pressure maintenance.&apos; These increments are suitable for these simple cases. They are, however, inadequate for reservoirs with time dependent drive mechanisms including water drive. A time increment removes this inadequacy and is

By T. P. Floridis, J. H. Young

The need for close control of the phosphorus content of steels has led to numerous investigations on the equilibria of the dephosphorization reactions. Winkler and chipman1 have established the general conditions for effective dephosphorization of steel. They are high slag basicity, high oxygen potential, and low temperature. Other investigators have made additional contributions to the understanding of the dephosphorization process. The current status of the understanding of the dephosphorization of steel is concisely presented by Bodsworth2 and by Ward. The investigation reported in this communication was undertaken with the purpose of establishing the effect of additions of barium oxide and calcium fluoride on the dephosphorizing capacity of slags. Esin and Gel&apos;d4 proposed that barium oxide, being more basic than calcium oxide, should cause an increase in dephosphorizing capacity when added to steelmaking slags, or when used as a substitute for calcium oxide. Derge5 has also proposed that in the future conventional slags might be replaced by BaO-Al2O3 slags. There is, however, no experimental evidence confirming the effect of barium oxide on the dephosphorizing capacity of slags. The effect of calcium fluoride on the dephosphorization of steel is not clearly understood. It is generally recognized that additions of calcium fluoride are beneficial. It is not clear, however, whether calcium fluoride affects the equilibrium of the dephosphorization reaction, or whether it simply causes an increase in the fluidity of the slag and, consequently, faster approach to equilibrium. The experimental procedure consisted in equilibrating synthetic molten slags with liquid copper at 1550°C under a gas stream containing argon, hydrogen, and water vapor. In all experiments the argon to hydrogen ratio was approximately 4:1, and the hydrogen to water ratio was 5.42:l. Molybdenum crucibles were used as containers for the slag and metal. Under the above-described conditions of temperature and composition of atmosphere, there was no observable attack of the crucibles by the metal, slag, or atmosphere. Copper was used instead of iron, because iron attacks molybdenum. The equilibration was made in a tubular furnace consisting of a recrystallized alumina tube. The alumina tube was heated by electrical resistance. A Pt-40 pct Rh wire winding was used for most runs. A silicon carbide tubular resistor was also used for some runs. Temperatures were measured with a Pt-Pt-Rh (10 pct Rh) thermocouple and kept constant within ±5°C. Equilibrium was approached from both sides, i.e., by adding the phosphorus either as oxide in the slag or as a phosphorus-rich alloy of phosphorus and copper. The holding time at the equilibrium temperature was 6 hr. At the end of each run the crucibles were rapidly cooled and removed from the furnace. The slag and metal were separated and analyzed. The experimental results are shown in Table I. The phosphorus content of the slag is expressed both as percent phosphorus pentoxide and as percent phosphorus. The basicity ratio is computed by dividing the number of moles of basic oxides-oxides of barium, calcium, magnesium, and sodium—by the number of moles of acidic oxides- oxides of aluminum, phosphorus, and silicon. Calcium fluoride is not included in the computation of the basicity ratio; i.e., calcium fluoride is assumed to be neither basic nor acidic. The distribution ratio of phosphorus—percentage of phosphorus in the slag divided by the percentage of phosphorus in the metal- is plotted in Fig. 1 against the basicity ratio. The results indicate that slags containing barium oxide have greater dephosphorizing capacity than slags containing calcium oxide. The high dephosphorizing capacity of slags containing sodium oxide and the low dephosphorizing capacity of magnesia-containing slags which already have been reported in the literature2 are confirmed by the results of this investigation. It appears that calcium fluoride has a beneficial effect on the distribution of phosphorus between slag and metal in acid slags only. Although the obtained distribution ratios between the phosphorus contents of slag and copper are not directly applicable to the dephosphorization of steel, they are sufficient for evaluating the effect of slag additions on the dephosphorizing capacity of slags in general. An increase in the ratio of distribution of phosphorus between slag and metal indicates lowering

Jan 1, 1968

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

By J. S. Aronofsky, A. S. Lee

Results and experimental procedures are presented covering a preliminary laboratory investigation of the compaction of reservoir rocks and its effect on porosity and permeability. "Egective" compressibility was measured by subjecting core material to an overburden load and reducing pore pressure. Preliminary results showed relatively high effective compressibilities which varied from 1.8 X 10-&apos; pore volume/pore volume /lb / in.~ for limestones to 7.7 X 10-6 pore volume/pore volume/lb/in.&apos; and even higher for sandstone reservoirs conmining large amounts of fine clay material. It appeared from the initiol results that the effective compressibility of the material could not be correlated directly with porosity and that other factors, such as the amount of clay material present might have to be taken into account. The work to date has indicated that effective compressibility factors will have to be measured for the particular reservoirs heing studied. Oil permeability of core materid was measured under various effective overburden loads from 0 to 8,000 psi. It has been found than reduction of permeability in clean sands was relatively small and the results agreed with published data. For sandstones containing large amounts of clay, preliminary tests indicated very large reductions in permeability with increasing effective overburden pressures. It is planned to continue laboratory work on this phase because of its importance in low-permeability reservoirs. INTRODUCTION During the past few years increasing interest has been shown in the differences obtained between conventional laboratory measurements on cores at atmospheric pressure and those when reservoir conditions are simulated. Since these data are used as the basis for calculations and the prediction of reservoir behavior, their evaluation under reservoir conditions is most important. The effect of the compressibility of the rock upon the reservoir behavior, as fluid pressure declines, is an important subject which has been insufficiently studied. The total pressure on any plane through a reservoir is the result of the grain-to-grain rock pressure due to the overburden and the pressure of the interstitial fluid on the plane. As reservoir fluid pressure declines, the net load on the rock phase must increase, and the result is the compaction of the rock structure which produces a decrease in pore volume. Simultaneously, the rock grains expand into the pore space as the fluid pressure declines. The result of these two effects is defined as the effective compressibility of the rock and is expressed in units of pore volume/original pore volume/psi. Work was started by Imperial in 1954 on the effects of pressure on the porosity of reservoir rock. These studies established effective compressibility factors for some limestones and dolomites. Since that time effective compressibilities have been obtained for other Canadian and some U. S. reservoir rocks. In conjunction with the study of porosity, an investigation has also been initiated to determine the effects of pressure on permeability. One outcrop and several reservoir sandstone cores have been tested to date. ROCK COMPRESSIBILITY Apparatus anD Procedure A diagram of the apparatus used in these studies is shown in Fig. 1. The equipment was constructed so that a uniform pressure, equivalent to the reservoir overburden, could be applied by the oil pump and transmitted on all sides of the core through the Lucite sheath. The sample was completely saturated by circulating brine through the mounted core. Pressure in

By H. M. Kraner, R. C. Devries, K. H. Gee, E. F. Osborn

On the basis of liquidus measurements in the system COO-Mg0-Al2O3-Sio, and previously published data, diagrams have been constructed at 5 pct Al2O3, intervals from 5 to 35 pct Al2O3,. Liquidus temperatures and primary phase fields are shown. The optimum composition of a blast furnace slag for a given alumina content is indicated. At the optimum point, ordinary slags will be entirely liquid and will have maximum desulphurization potential and minimum viscosity. The relation of optimum composition of slags to the "plateau region" of the liquidus surface, and the application of these data on synthetic quaternary slags to actual slag compositions are discussed. Index of refraction of glasses is given as well as composition, temperature, and phase data for each mixture. THE usual blast furnace slag, as a first approximation, can be considered a mixture of the four oxides, CaO, MgO, Also,, and SiO,. Systematic, extensive data for the quaternary system, CaO-MgO-A1,0,-SiO, is therefore required for the understanding of the properties of such a slag as a function of composition and temperature. With sufficient data, it should be possible to fix unequivocably the relative amounts of lime, magnesia, and silica required for a given alumina content to result in a slag composition having optimum properties. Other constituents, such as FeO, MnO, Ti02, and S, have an effect on the properties of a slag, but as long as they are present in small and approximately constant amounts they produce only a second-order effect superimposed upon the major changes in properties of slags determined by the relative amounts of the four major components. Viscosity and desulphurization data have been reported for mixtures approaching blast furnace slags in composition, but systematic liquidus data have not been obtained. Inasmuch as a slag must be all liquid in order to be most effective as well as practicable, clearly the temperature above which a mixture is all liquid (liquidus temperature) is a type of data needed. Such data have been obtained through the study of 446 compositions and are pre- sented in this paper along with a discussion of their bearing on the optimum composition of blast furnace slags. For an orderly presentation of the data, the quaternary system is viewed as a tetrahedron with one component at each apex. Fig. 1 shows a tetrahedron representing the system Ca0-Mg0-A1,0,-Si0,. The base is the ternary system Ca0-Mg0-SiO,, A1,0, is the top apex, and the front face, the system CaO-

Jan 1, 1955

By J. H. Keeler

The tensile characteristics of Zr-Fe binary alloys containing up to 5 atomic pet Fe are reported for the temperature range —195o to 500°C. A linear relation between stress at constant strain and volume fraction ZrFe2 was found. The coincidence of data from unalloyed zirconium with zero volume fraction ZrFe2 indicated little or no solid solution in IL-zirconium, in agreement with Hayes, Roberson, and O&apos;Brien.&apos; The absolute increase in strength due to particle strengthening, although decreasing with increasing temperature, was a greater percentage at high temperature. ZIRCONIUM is of interest for use in nuclear reactors because of its low neutron absorption, good corrosion resistance, and high melting temperature. The alloying of zirconium with iron has been considered as a means of increasing the mechanical strength of zirconium without seriously increasing the neutron absorption " over that of unalloyed zirconium. The Zr-Fe system has a eutectic at 934°C and 23.7 atomic pet Fe and a eutectoid at 800°C and 4.0 atomic pet Fe. The zirconium-rich end of this system determined by Hayes, Roberson, and O&apos;Brien&apos; is shown in Fig. 1. The intermetallic phase coexisting with a and ß-zirconium has been reported as Zr2Fe3,1 with a,, - 7.04A, and as ZrFe2,2 face-centered-cubic, the phase being of the MgCu, type (C-15). It was more recently agreed to be ZrFe33 and face-centered-cubic. This intermetallic phase is essentially insoluble in a-zirconium, the hexagonal-close-packed modification; and the lack of solubility makes the system particularly interesting metallurgically. The system is strengthened almost exclusively by particles of in-termetallic phase, and there is very little solid solution strengthening to complicate the analysis. The Bureau of Mines, in its survey of zirconium-base alloys,&apos; reported the tensile properties of Zr-Fe alloys made from chloride process zirconium, induction melted in graphite crucibles, and swaged at 850°C in iron sheaths. Additional data on these ZrFe alloys were given by Hayes, Roberson, and O&apos;Brien.&apos; Chubb and Muehlenkamp% have recently reported the strength of Zr-Fe alloys containing up to about 1.25 atomic pet Fe. These alloys were made from crystal bar zirconium, hot worked at 820°C, annealed at 700°C, and tested both at room temperature and at 316°C. Experimental Procedure The materials used in this investigation were high purity zirconium made by the iodide process and electrolytic iron. The composition of the zirconium as obtained by spectrographic analysis and the nominal composition of the iron are given in Table I. Alloy ingots weighing 100 g were made by are-melting under argon in water-cooled copper crucibles in a multihearth furnace."

Jan 1, 1957

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3&apos;, as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By G. S. Cole, G. F. Bolling

ThE exact type of fluid flow which occurs in a solidifying ingot is important in determining subsequent grain structure. This has been shown in studies of natural Convection" and of forced stirring or other disturbances of the melt."16 We shall explicitly argue that a complement to the existing natural flow in an ingot should be more effective than other types of flow in promoting the columnar-to-equiaxed transition. The ultimate effects of fluid flow upon structure is one of the topics of solidification that we have investigated in the alloy system Pb-Sb, under conditions simulating casting. In Fig. 1, the essential features of a bidirectional growth apparatus are shown; horizontal freezing from water-cooled faces within a low-thermal-conductivity lavite boat is a reasonable simulation of an ingot section. Details such as the furnace and thermocouples are omitted in order to show the location of four permanent. magnets, each with a pole separation of 21 in. providing a central field of about 1000 Gauss. When coupled with a dc current imposed through appropriate connections made at the cooled faces, a flow of fluid is produced as shown schematically. This technique described by Pfann and ~orsi" is ideal for our purpose since the flow indicated is the same as that we observe to occur naturally in this system. Components of 99.999 pct purity were used for study and all due precautions were taken in alloy preparation to avoid contaminants. Sections of the specimens were taken to ensure results representative of the interior as well as the surface of specimens. All proportions of equiaxed and columnar regions were measured by tracing the etched grain structures onto graph paper and simply counting squares. Four alloys were examined at superheats of 40" * 5°C and 100" * 9°C. Preliminary tests had shown that no appreciable enhancement of structure was obtained with magnetic field alone, so that this condition is not reported; it should nevertheless be noted that other configurations of magnetic field will reduce convection and thus enhance columnar growth.&apos;8 For the tests reported the magnetic field was applied to a specimen by bringing the four preassembled magnets to a position 2 mm from an outer tube immediately after the ingot was poured. The dc current of 30 amps passed through the sample throughout the entire solidification cycle, resulting in a power dissipation of 9 w per sq cm of interface. This may be compared to the evolution of latent heat of approximately 18 w per sq cm. Table I contains the results of this experiment in terms of the total area ratio, equiaxed/columnar grains, as a function of the field interactions, solute concentrations, and superheats employed. The total structure of the ingot is seen to be most influenced when both the field and current are applied simultaneously; when current acts separately, little effect may be noted in spite of the heat supplied. In addition, the change in structure from the no field-no current case to the field-current condition is more pronounced at the higher superheat, and the higher the concentration of antimony. An example of the grain refinement, as well as the increased equiaxed zone, is shown in Fig. 2. It is now important to prove that there is indeed an increase in fluid flow due to the presence of the field-current interaction; this is done by temperature measurements in the liquid metal. Let us consider a bidirectional casting in which heat is applied to and removed from the system, in such a way that rate of solidification is zero.* When a sensitive thermocouple

Jan 1, 1967

By Ralph H. Sweetser

C. H. Herty, Jr.,* Pittsburgh, Pa.—The procedure of the Open-hearth Committee in studying pig iron and its effects in the open hearth has been influenced by the discussions at a number of meetings of the Committee. Those discussions have brought out very clearly that, as far as the pig iron affects the quality, interference with quality should be studied for three definite types of pig iron: (1) low-silicon pig iron; (2) very high-silicon pig iron, and (3) pig iron in which the silicon varies over a wide range in short periods, such as 1 to 3 casts. If a blast furnace is running steadily at 1 per cent. silicon iron, practically no trouble, apparently, can be traced to the pig iron, but if the furnace is running from 0.60 up to 1.50 and then down to 0.60 per cent., trouble in the finished steel is liable to occur, which apparently cannot be corrected by open-hearth practice. The open-hearth discussions have shown fairly definitely that with low-silicon iron, one type of trouble arises on the finished product and with the high-silicon iron, another. Our experience with the high-silicon is that any non-metallic matter that may form, does so when the pig iron is put into the furnace; that is, silicates immediately form which are more liable to be high in silica than would happen with low-silicon iron. I think Mr. Sweetser will agree with mc that if a blast furnace is very irregular, different points in the furnace may be working irregularly, in other words, the temperature gradient all over the furnace is not uniform. We have made many determinations on that point which indicate that a varying blast furnace causes hot spots and cold spots around the periphery. If some of those spots are hot and others are cold, although the analysis of the iron may be constant, then unreduced oxide, going through on one side, and good iron, going through on the other, may mix and the average temperature of the iron is not high enough to get completely rid of the oxides. So our method of attack is directly on that point; it is our first objective. Our procedure is to make a number of consecutive tests at a blast furnace, making a detailed study of the blast-furnace operation. We follow the iron through the open-hearth heat, being sure that we know just how much of each kind of iron gets into the open hearth, and take out specified samples at certain times during the process, working on steel where no finishing additions are made in the furnace. We are following one type of iron through the billet mills and into the finished product and are obtaining complete data on open-hearth operation. Besides the ordinary chemical analyses on the samples of slag and metal, we are running samples of the plg iron, the steel in the open hearth and the finished steel, for oxygen and silicates. We are going to find out whether or not oxygen, as silicates or oxides, has some connection with this trouble. If not, we may be able to locate some other factor. I am inclined to think that the silicates are responsible, judging from the indications in some other work that the Bureau of Mines is doing in Pittsburgh. We have laid out a very definite method of testing to which we will adhere at the different plants where we are now working and at others in the future. Our aim is to

Jan 1, 1927

By AIME AIME

ALFRED WILLIAM GAUGER ??Al" or &apos;?Doc" to his many friends in the coal and chemical industries- is known for his research talents and organizing ability. Appropriately the first public recognition of his technical ability was by the A.I.M.E. in the publishing of a paper by George A. Burrell and Alfred W. Gauger in the "Transactions" for the year 1916. "Al" Gauger was born at St. Paul, July 31, 1892. He graduated in chemistry at the University of Minnesota in 1914. A year later he began his initiation into the mysteries of coal mining when he joined the safety division of the U. S. Bureau of Mines at Pitts- burgh, serving from 1915 to 1917.

Jan 1, 1944

By Robert Hamilton Morris

FATE, rather than planning, put Bob Morris into coal mining. He was a farmer&apos;s son, born at Plattsburg, Ohio, just 68 years ago (Feb. 28, 1878) though he could easily pass for ten years younger. Before he was ready for high school the family moved to Columbus, seat of Ohio State University, whose course in mining engineering attracted him because lie thought it the broadest of the engineering courses. He really wanted to be a steel metallurgist but it was a coal-mining company that offered him a job when he graduated, and this circumstance directed his entire future professional life. To. be sure it wasn&apos;t such a glorious opportunity so far as pay went -$40 a month-but his employer, the Modoc Coal & Mining Co., Modoc, Ohio, was developing a new shaft mine, thus offering some good experience. In 1902, after a year&apos;s experience, he was made superintendent of the property. Then in 1903 the Continental Coal Co. at Glouster, Ohio, offered him a better job as their chief engineer, which he retained until 1905, at the same time joining the A.I.M.E.

Jan 1, 1946

By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation&apos;-&apos; despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By S. S. Arentz

PLANNED health and safety programs have become an essential part of American industry because such programs lead to increased operating efficiency, improved labor relations, better public relations, and to substantial savings in compensation insurance. Those of you who have had the unpleasant duty of informing the wife or widow of one of your men of his serious injury or death while on the job, know that all the benefits of a successful safety program do not show on the balance S. S. ARENTZ, Member AIME, is General Superintendent, Nevada Operations, Combined Metals Reduction Co., Pioche, Nevada. AIME San Francisco Meeting, February 1949. TP 2741 A. Discussion of this paper (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Jan. 6, 1949. sheet. These programs are of particular importance to the mining ,industry because mining&apos;s reputation as an unusually hazardous industry and the commonly isolated location of mining operations tend to focus attention on these problems. Description of Operations: Before proceeding with a discussion of our health and safety programs at Pioche, it may be proper to give a brief description of Pioche and of our operations there. Pioche is one of the early Nevada mining camps. It was founded shortly after the discovery of high grade silver ore in 1863 and mining has continued with more or less regularity to the present day. In an era of lawlessness, Pioche was notorious. The story persists that 75 men died with their boots on before one died a natural death, and old payroll records show that nearly as many gunmen were employed to stand off claim jumpers as there were miners working the mine. That was probably as close to a safety program as the times permitted. Pioche is situated in southeastern Nevada on the main highway between Ely and Las Vegas. The camp is on the flank of "Treasure Hill," near the original silver discovery, at an elevation of about 6000 ft. The present day population of about 2000 is primarily dependent upon the mines of the area, although Pioche also serves as the county seat of Lincoln Couqty and as the center of the surrounding livestock industry. The camp is served by a branch of the Union Pacific Railroad and receives power from the generators at Hoover Dam. The Pioche operations of the Combined Metals Reduction Co. were started in 1923 when the first complex lead-zinc ore was shipped to the company&apos;s mill at Bauer, Utah. The modern mill at Pioche was completed in 1941. The operations are medium sized in the nonferrous field, employing an average of 350 men in the mine, mill, and related works. The complex lead-zinc ore is mined from replacement deposits in a comparatively flat, extensively faulted, limestone horizon. Mining methods vary from stull-supported open stopes to filled square-set stopes. The thin bedded limestone and shale overlying the ore is allowed to cave as areas are mined out and caving frequently follows closely upon ore extraction. The relatively heavy ground and the numerous faults add to the problems of safe mining. The mine is well mechanized and the mill and surface plant are modern and well equipped. Labor is organized in a C.I.O. union and labor-management relations have been unusually harmonious. During most of the period since 1923 a competent supervisory staff worked to reduce safety hazards but the primary responsibility for safety rested on the individual workman. Accidents happened and all too frequently they were regarded by all concerned as unavoidable. In October 1939, the late Robert L. Dean became superintendent at Pioche. Most of his previous experience had been in the fields of iron and coal mining and from that experience he brought the concept that no accident is unavoidable. Many of the features of our present health and safety programs were initiated by Mr. Dean during his term as superintendent. Health Program: Our health program centers in Dr. Q. E. Fortier and his new, well-equipped, and well-staffed, modern hospital in Pioche. The program starts with a thorough pre-employment physical examination and is followed by yearly re-examinations at the expense of the company. The Pioche Mutual Benefit Association, to which all Pioche mine operators and employees belong, pays benefits covering hospitalization and surgery expense incurred by employee members and their families. The Association is governed by a board of directors elected by its members. The mine operators of the district donated the original capital and pay the monthly dues of the employee members. The employees pay the dues covering members of their families. Though not strictly a part of the

Jan 1, 1951

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,&apos;, &apos; were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.&apos; Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951