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By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By H. J. Ramey

A general solution is presented for the transient temperature distribution caused by radial movement of a cylindrical heat source through a homogeneous medium of infinite extent. This problem represents a highly simplified model of the movement of a combustion front during the thermal recovery of oil. Numerical solutions are presented for a heat source moving at a constant velocity, and a velocity inversely proportional to the radial location of the heat source. Numerical solutions are presented for both finite and infinite vertical thickness of the heat source, i.e., with and without vertical heat losses. The numerical solutions are used to estimate the fuel concentration needed to maintain a combustion front during the thermal recovery of oil. The sensible heat carried to the combustion front by the injected gas stream is discussed in regard to the fuel concentration. Numerical solutions for a heat source (combustion front) of finite vertical thickness indicate the field conditions that may be necessary to sustain the temperature of a combustion front above the ignition temperature of the fuel over considerable distances from an injection well. The results also have implications in regard to the quantity of heat required during ignition. The results of this computation apply to a highly idealized model of a thermal recovery process. But the results may be used as a guide in engineering consideration of the thermal recovery process. INTRODUCTIO N The thermal recovery of crude oil has received considerable attention since the publication by Kuhn and Kochl of laboratory and field tests of this method of oil recovery. Other publications2,3,4,5,6, since that time have dealt with various features of the thermal recovery of oil and have illustrated the extremely complex nature of this process. Vogel and Krueger7 described an electric analog computer designed to solve a moving heat source problem which was analogous to movement of a combustion front during the thermal recovery of oil. The heat source was maintained at constant temperature and was a cylindrical source of infinite height (no vertical heat loss) moving radially at either constant velocity, or at a velocity inversely proportional to the radial location of the heat source. Jenkins and Ramey2 presented analytical solutions to a similar heat conduction problem and pointed out the possible importance of vertical heat losses. The following presents a general solution to the transient heat conduction problem introduced by Jenkins and Ramey4 as well as numerical solutions for a wide range of conditions possibly similar to those that might exist during field operation of the analogous thermal recovery process. DESCRIPTION OF PROBLEM The problem considered in this paper is determination of transient temperature distribution caused by a cylindrical heat source of infinite or finite vertical height, moving radially through an isotropic medium of infinite extent. It is further assumed that the heat flux generated at the surface of the moving heat source may be a function of time such that the fuel concentration required may be constant, or permitted to vary, and that heat is generated at the surface of the heat source only. In regard to the thermal recovery of oil the assumption that heat is generated at the surface of the front is equivalent to assuming that the thickness of the combustion zone is infinitely small, or that the reaction rate between fuel and oxidant gas is infinite. The last assumption does not appear stringent. See laboratory information published by Martin, et al3 Under these assumptions the temperature distribution throughout an infinite medium caused by a heat source moving radially with an arbitrary velocity may be described by The heat generation function or heat flux at the surface of the source, +(t), is Note that the fuel concentration may be defined as a function of time. Eq. 1 is derived in the Appendix.

By K. D. Sheffler, R. W. Hertzberg, R. W. Kraft

The Ni-Ni,Ti lamellar eutectic alloy responds to unidirectional solidification by alig-nment of the platelets of the two phases roilghly perpendicular to the moving solid-liquid interface. X-ray diffraction and zetallographic experimenls show that the following cryslallographic relationships exist in the directionally solidified ingots: lamellar interface w [0001] Ni3Ti 11 (111 }Ni local growth direction (1120) Ni3Ti n (110) Ni These relationships are rationalized on the basis of the crystallography of the constituent phases. In recent years researchers in several laboratories have shown that an aligned or "controlled" micro-structure can be produced in many binary eutectic alloys by forcing the alloy to solidify unidirectionally in an elongated crucible.'-3 It also has been found that a unique crystallographic relationship often develops between the two phases in such a structure.4, 5 Since a parallel arrangement of phase particles in an alloy should, and, in many cases, does, produce unique and highly anisotropic properties, the alloys so produced are of potential interest in a variety of applications. Studies of these alloys are also of interest at the academic level because they help to improve our basic understanding of the way in which metals solidify. This paper reports the metallographic and crystallographic structure of another of these alloys—that between nickel and Ni3Ti. In a separate paper, hot tensile and stress rupture properties as well as deformation and fracture behavior of the same alloy are discussed.19 EXPERIMENTAL DETAILS AND RESULTS General Characteristics of the Eutectic Reaction. Several small exploratory Ni-Ti melts were made to resolve a conflict in Hansen6 over the eutectic composition. The alloy containing 16.4 at. pct Ti, Fig. 1, appeared metallographically to be closest to the eutectic composition, although small dendritic patches of proeutectic nickel are present. The eutectic morphology is lamellar and appears quite sharp and angular, indicating a strong influence of crystallographic factors upon the microstructure. Some of the eutectic nickel platelets are continuous with the primary phase, whereas in hyper eutectic melts a "halo" of nickel generally surrounded the proeutectic inter-metallic platelets, indicating that nickel is the nucleating phase in this eutectic reaction. Extensive precipitation of Ni3Ti has occurred in the primary nickel phase in a Widmanstatten pattern which makes the dendrites difficult to differentiate from the eutectic mixture. This phenomenon may account for discrepancies among the eutectic compositions reported in the literature. The sloping solvus line bounding the nickel primary solid solution explains the presence of the intermetallic precipitate. Poole and Hume-Rothery7 report that the solubility of titanium in nickel drops from 13.8 at. pct at the eutectic temperature (1304°C) to approximately 9 at. pct at 700°C (Ni3Ti, on the other hand, melts con-gruently and exhibits essentially no solubility for nickel or titanium). Lever rule calculations based upon Poole and Hume-Rothery's phase diagram indicate an increase from 21 vol pct Ni3Ti in the eutectic mixture at the eutectic temperature to 61 pct at room temperature. Selective point count measurements of the volume fraction of eutectic Ni3Ti platelets in the eutectic microstructure yielded a value of 46 i 2 vol pct, which required extensive precipitation of Ni3Ti from the nickel solid solution onto the eutectic intermetallic platelets during cooling from the solidification temperature. Influence of Directional Solidification. Nickel bar and titanium sponge of 99.9 pct purity were induction-melted in zirconia crucibles under argon in the proportion of 13.8 wt pct (16.4 at. pct) Ti to produce 14-lb master heats which were cast into investment molds yielding 5/8-in.-diam pins approximately 10 in. long. These pins were remelted under argon in horizontal zirconia boats and unidirectionally solidified to produce 1/2-in.-sq ingots approximately 44 in. long. Details of the experimental techniques and apparatus are described elsewhere.'

Jan 1, 1970

By S. K. Mitra

A refinement of the Seeger model for intersection process is investigated which is in better agreement with experimental observations than the original. It is shown that, in single crystals, the strain hardening in Stage II is mainly due to the short-mnge interactions when intersection is the rate-controlling process. It is also demonstrated that the creep curves, as predicted by this theory, are in good agreement with the experimental observations. MOTT: Cottrell? and Seeger have developed an approximate theory for plastic deformation of single crystals over the range of variables where the strain rate is controlled by the rate of intersection of dislocations. Although it is now generally agreed that the low temperature deformation of many pure metals is controlled by the intersection mechanism, various dictates of the over-simplified Seeger model are not in good agreement with all the experimental facts. It is the purpose of this paper to reveal that by appropriate extensions of the Seeger model, particularly those suggested by Basinski: a much more reliable theory results. The refined model to be presented here will be shown to account, in a satisfactory way, for the effect of stress, temperature, and strain on the creep rate under constant stress and for the effect of temperature and strain on the flow stress in constant strain-rate tests. EXPERIMENTAL METHOD To Check the theoretical deductions, both creep and tension tests were conducted on single crystals of high-purity Al (99.994 pct Al) so oriented that both the active slip plane and the Burger's vector of the operative dislocations on that plane made angles of about 45 deg to the tension axis. Single crystals of aluminum (5/8 in. by 1/10 in. by 8 in.) were grown in a graphite mold under an inert atmosphere using the Bridgman method. The chemical composition of the aluminum is given in Table I. A common seed was used for all crystals and their orientation is shown in Fig 3. The extensometry consisted of two differential transformers with matched outputs mounted so as to measure the extension in a 2 in. gage length. The amplified difference in output of the two transformers was recorded by a potentiometer. The amplification was calibrated before each run so that one chart division of the recording potentiometer indicated a 105 shear strain on the specimen. Stresses were measured to the nearest 1 x l04 dynes per sq cm. ACTIVATION VOLUME The concept of Basinski that the activation volume is not constant but is a function of the force that aids thermal fluctuation in effecting the cutting of dislocations will be adopted in this section. The force acting due to an applied shear stress on the dislocation being intersected is where L is the mean spacing between the forest dislocations, is the Burger's vector and T is the back stress. A detailed discussion about the origin of back stress will be taken up later in this report. As shown by Basinski, the activation energy, U, that must be supplied by a thermal fluctuation in order to effect intersection, is equal to where x is the distance through which the dislocation must be translated for complete intersection, and Fm is the maximum force encountered in intersection. When the applied stress is decreased abrupt ly F also decreases and the activation energy increases correspondingly as documented in Eqs. [ 1 ] and [2]. The Seeger equation for the strain rate when the deformation is controlled by rate of intersection of where the shear strain rate (per sec) N = the number of points per unit vol at which intersection can take place

Jan 1, 1962

By W. D. Robertson

SINCE the comprehensive paper of Moore, Beckin-sale, and Mallinson,' little consideration has been given to the mechanism of mercury stress cracking of copper-base alloys, apart from extensive work on metallurgical and fabrication variables employing mercurous nitrate as an evaluation test. However, with the phase diagrams now available and the recent considerations of interfacial tension at grain boundaries, developed by Smith,2 it appears that the elements of a detailed solution to the problem are available. The facts that require explanation are: 1—Pure copper is not embrittled by mercury, with or without an applied or residual stress. 2—Cu-Zn and other copper-base alloys, in excess of some undefined solute concentration, are embrittled provided an external or residual stress is acting; cracking is not observed in the absence of stress. 3—The path of fracture is invariably intergranu-lar. 4—Copper and copper-base alloys do not dissolve readily in mercury at room temperature.' Consideration of the Cu-Hg phase diagram% hows that, at room temperature, solution of copper in mercury is probably limited by the formation on the surface of a microscopically thin layer of inter-metallic compound, CuHg, having a very limited range of solubility which effectively restricts diffusion of copper and mercury. But, above 150°C (the highest peritectic temperature) copper solid solution is in equilibrium with a liquid Hg-Cu solution and, consequently, copper should dissolve freely in a large volume of mercury with the formation of an equilibrium dihedral angle at grain boundaries in contact with the liquid phase. Depending on the magnitude of this angle, mercury will or will not penetrate the solid phase along grain boundaries and spread over grain faces. Thus the measurement of the dihedral angle of grain boundaries in equilibrium with the liquid phase above 150°C should indicate whether copper is intrinsically resistant to embrittlement by mercury. In view of the fact that mercury is appreciably soluble in copper, it may also be anticipated that diffusion of mercury will take place at higher temperatures in the absence of the intermetallic compound and possibly at a more rapid rate along grain boundaries than through the grains, resulting in a Cu-Hg alloy of unknown properties. In the case of brass, the ternary system Cu-Zn-Hg is involved and, from the resistance of brass to general solution in mercury at room temperature, it is probable that a compound of limited solubility range also exists, similar to the binary Cu-Hg sys- tem. Also, compared with copper, a change in the dihedral angle at grain boundaries in contact with mercury may be expected to result from the addition of zinc to copper. The preceding generalizations appear to be confirmed by the following experiments. Experimental Results Oxygen-free copper wire, annealed at 700°C for 3 hr in copper foil, was immersed in mercury at 170°C, with and without an applied stress. After 24 hr immersion, specimens which were spring loaded to a nominal stress of 10,000 psi had not failed, and there was no apparent embrittlement as indicated by a 180" bend around a diameter approximately equal to the diameter of the wire (0.125 in.) : General solution of the surface had taken place, indicated by a change in diameter of the wire, and the resulting structure of the surface is shown in Fig. 1. It is apparent that angles have developed at grain boundaries and examination at a high magnification indicates that the angle is in excess of 120°, completely excluding penetration of mercury. In view of the measurements made by Smith n the

Jan 1, 1952

By J. O. Brittain, E. Lautenschlager

Yield point measurements were made on polycrys-talline specimens of a iron deformed various amounts at 770, 1950, or 273°K, aged, and redeformed at 77: 195°, or 273°K. When the prestrain temperature is lower than that subsequent to aging, the yield point return is suppressed relative to specimens deformed at the same temperature both before and after aging. The degree of suppression is a function of both the magnitude of prestrain at the lower temperature and the difference between the deformation temperatures before and after aging. It is proposed that the suppression is caused by the formation of dislocation barriers during the initial low-temperature deformation. The aging kinetics of polycrystalline a-iron wires deformed at 77o or 303oK were studied at 44 " and 64 "C using internal friction measurements. No change was noted as a result of the difference in prestrain temperature. IN an earlier investigation1 it was observed that the return of the yield point was suppressed when a poly-crystalline specimen of a iron was plastically deformed at 77oK, aged at room temperature, and subsequently tested at room temperature. In order to investigate this observation, a research program was undertaken to measure the effect of prestrain temperature on the strain aging of a iron.' According to Thomas and Leak,3 return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solution, while the return of the yield point as a function of aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,4 the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point upon restraining. In this experiment, both methods of measuring strain aging were employed in order to have two independent measurements of the strain aging phenomenon. In a previous study,5 the strain aging kinetics of a similar lot of a iron were measured for specimens which were prestrained and tested at the same temperature over the range of 77" to 273°K. Although some differences were found in the correlation of the two methods employed for measuring strain aging, the kinetics of strain aging were unaffected by the change of prestrain and test temperature. In another study,6 dislocation line tension and the density of the solute atmosphere were found to contribute to the return of the yield point when ingot iron specimens were prestrained at 303°K and tested at a lower temperature, namely 77°K. This paper is concerned with changes in strain aging kinetics produced by pre-straining at 77" to 303°K and testing at either the prestrain temperature or at higher temperatures up to 273°K. EXPERIMENTAL PROCEDURE The polycrystalline a iron specimens used in both the tensile and internal friction tests were 0.033-in. diam ingot iron wires, wet hydrogen treated and re-carburized. A more detailed procedure for processing a 3/16 in. ingot iron rod (nominal wt. pet composition: Fe - 0.013; C - 0.0125; Mn - 0.023; Si -0.005; P - 0.0023; S - 0.11; Cu - 0.004 N) to 0.033 in. diam specimens containing approximately 0.020 wt pet C and no detectable nitrogen with a grain diameter of 0.033 to 0.040 mm is given elsewhere.5 Immediately prior to testing, specimens were solution treated for 15 min at 700o ± 2°C in a static vacuum of less than 50 ?. of Hg and rapidly quenched into an ice-water bath while still enclosed in a 3 mm quartz vial. The internal friction specimens had 8-in. gage lengths and the tensile specimens had 2-in. gage lengths. The wires used as tensile specimens were first run as internal

Jan 1, 1962

By M. T. Hepworth, W. B. Sample

HYDROGEN solubility and linear contraction measurements were made at constant temperature on an alloy of titanium of constant oxygen-to-titanium molal ratio but variable hydrogen content. A cylindrical specimen of titanium (0.25 by 1.6 in.) containing 0.75 at. pct 0 and less than 0.03 at. pct N was cast from a master button of iodide process titanium which had been alloyed with titanium dioxide. Four vacuum fusion analyses, which were made along the length of the cylinder after the hydrogen solubility studies were made, revealed a variation of oxygen content of less than 0.02 at. pct. The specimen was introduced into a quartz furnace tube, annealed and outgassedat 1050"~ for about 1 hr, and then held at 800" * 0.5" for about 30 hr, during which latter time experimental data were taken. The leak rate to the furnace chamber was not sufficient to contaminate the specimen during the run as determined by leak-rate studies and vacuum fusion analyses for oxygen and nitrogen before and after the runs. The furnace chamber was attached to a modified Sieverts apparatus used to introduce measured quantities of purified hydrogen to the specimen. A quartz pushrod transmitted changes in length of the specimen to a Chevenard dilatometer. The push-rod passed through a vacuum grease seal to the dilatometer which amplified motion of the rod by a factor of 319. During hydrogen addition, the pushrod did not contact the specimen. Measured quantities of hydrogen were added to the specimen and equilibrium hydrogen pressures recorded as a function of hydrogen content. The solubility data, which appear in Fig. 1, agree well with a separate investigation made with a different apparatus. The solubility limit of the hcp a phase appears as an abrupt discontinuity in slope at 3.4 at. pct H. The solubility plot has been extended as a dashed line at this discontinuity in order to emphasize the discontinuity. The hydrogen content at which bcc P appears is not clearly defined. An arrow indicates solubility data were taken upon hydrogen addition. Upon reaching the arbitrary maximum hydrogen content of the run, the quartz pushrod was pressed against the specimen in order to record the change in length with hydrogen removal. A pressure of about 100 g per sq cm was required to overcome the friction of the vacuum seal in order to obtain reproducible linear contraction data. The contraction ratio ~2/1", change in length divided by original length, was set equal to zero for the maximum hydrogen content. The relative contraction of the specimen was observed upon removal of hydrogen in the following manner. The system was opened to the pumps for a few seconds and an unknown quantity of hydrogen was removed. The system was then isolated from the pumps by closing a stopcock and allowed to return to equilibrium. When the temperature returned to 800°C, the pressure stabilized, and contraction ceased, measurements of contraction and pressure were made. The hydrogen content of the specimen was then deduced by measuring the equilibrium PIydrogen pressure and referring to the solubility plot. Linear contraction was then plotted against interpolated values of atomic percent hydrogen. The justification for this procedure is the established reversibility of the hydrogen equilibrium.' Uniaxial compression was assumed to have no effect on hydrogen pressure. The isothermal linear contraction data are plotted on Fig. 1. An arrow indicates data were taken upon removal of hydrogen. The solubility limits of the two phase a i /3 region can be identified by discontinuities ill slope of the dilatometric plot at 9.1 and 3.4 at. pct H, agreeing well with other studies.' Dashed extensions of the plots emphasize the discontinuities. Isothermal studies of expansion made upon hydrogen addition gave curves of much smaller slope and less pronounced discontinuities. A uniaxial compressive stress tends to accentuate volume changes in going from the more open bcc phase to the hcp phase.2 Incomplete data on ex-

Jan 1, 1962

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

Date of Congress: Sept. 20-25, 1915 The Committee on Local Affairs is fortunate in having secured for a period expiring on Oct. 17, an option. on 100 rooms at the Palace, St. Francis. and Fairmont hotels, the three leading hotels in San Francisco, with the distinct understanding that, on account of previous engagements whereby the hotels are reserved to their capacity, the rooms must be vacated on Sept. 25, 1915. The rates applying will be $7 per day for the court rooms occupied by two people, or $10 per clay for outside rooms occupied by two people. The outside rooms will face the main thoroughfares at the Palace and will face the city and bay at the Fairmont, which latter is situated oil a high hill. The St. Francis faces an open square and is flanked by main thoroughfares on two sides. If any members desire their reservation to extend either before the 20th or beyond the 25th, the Committee will use its best endeavors to secure such extension in individual cases, in accordance with the indicated wish. The Hotel Bureau in San Francisco is co-operating actively and closely with the. Committee on Local Affairs of the International Engineering Congress and offers the choicest rooms in any of 350 hotels other than the three mentioned above. This Hotel Bureau controls 50,000 rooms in San Francisco, which are all provided with hot and cold water, stationary basins, baths, house telephones, elevators, and bell boy service.

Jan 9, 1914

By N. L. Carwile, G. W. Geil

A metallographic study was made of deformation twinning (Neumann lamellae) in ingot iron slowly deformed in tension at —196O and —150°C. The results showed that twinning is initiated mainly during the initial stages of plastic deformation. However, the breadth of the twins generally increases with increase in strain up to fracture of the specimen. HE results of an investigation of the effect of low I temperatures on the flow, fracture, strain hardening, and strain aging characteristics, and the true stress-strain relationship for specimens of ingot iron deformed in tension were reported recently.1,2 In that study specimens of ingot iron, in different initial conditions, were slowly deformed in tension at various temperatures between —196" and +100°C. A phenomenon observed, but only briefly reported, was the formation of deformation twins (Neumann lamellae) in the specimens deformed at the lower temperatures. Preliminary metallographic examination of these specimens indicated that there was apparently some correlation between the deformation twinning and the strain of the specimen and that this factor merited further investigation. Some recent investigations have indicated a direct association of Neumann lamellae and the fracture of the metal. Bruckner".' * postulated that the twinning immediately precedes the fracture and the latter is initiated by the stopping of the propagation of twins, either at subgrain boundaries or at other structural features. Tipper and Sullivan5 postulated that Neumann lamellae are initiated by the shock or a shock wave set up at fracture in the still highly stressed unbroken metal, and that a high rate of deformation is a necessary condition for their formation. An extensive metallographic examination, therefore, was made of many of the specimens used in the study of ingot iron at this Bureau and of additional specimens deformed to selected strains under various conditions. The present paper summarizes the effects of deformation under these conditions upon the breadth and scope of the deformation twins. Other features of twinning will be discussed in another paper. Material and Testing Procedure All of the specimens were prepared from one lot of ingot iron, as hot-rolled, of chemical composition other than iron as follows: C, 0.02 pct; Mn, 0.02; P, 0.005; S, 0.018; Si, 0.002; Cu, 0.10; 0, 0.058; and N, 0.002. Cylindrical tensile specimens with a 2 in. gage length were used. The reduced section was slightly tapered from each end; the diameter (0.438 in.) at the midsection of the gage length was about 0.003 in. less than at the ends. The specimens were finished to the final dimensions by grinding and polishing in the axial direction. The ends of the specimens were machined with 3/4 in. x 10 threads and the shoulder fillets were machined to a radius of 0.75 in. The specimens were extended slowly in tension (deformation rate less than 0.5 pct reduction in area per minute) while immersed in an appropriate cryogenic liquid maintained at the desired temperature. The minimum diameter of the specimen was measured during the test by means of a specially designed reduction of area gage accurate to 0.0001 in." A detailed description of the testing equipment and the method of maintaining the desired temperature is given in a previous paper.' Each specimen, after deformation to a specified strain at a selected temperature, was sectioned longitudinally and examined metallographically. The preparation of specimens for metallographic examination was carried out in the usual manner by mechanical polishing and etching. Results and Discussion Deformation twins in specimens of ingot iron extended slowly in tension at —196" and —150°C are shown by the representative micrographs of Figs. 1

Jan 1, 1954

By Hans Lundberg

AFTER the war years, great activity has been shown in geophysical exploration for ore. The appreciation by mining and government geologists of geophysical techniques and results is largely responsible for the popularity of these methods. In Canada, plans are being made to study, by geophysical methods, the structure of a portion of the Pre-Cambrian shield in the hope that such studies will not only give a clearer picture of the geology, but will be of direct aid to the mining companies when selecting areas for detailed prospecting. Although geophysics thus has become more popular, some engineers are still reluctant to employ the methods to their full extent. Allotted funds are often rather low, so that the least expensive

Jan 1, 1947

By AIME AIME

THE first meeting" of the Iron and Steel Division was held Tuesday afternoon, Feb. 17, with nearly 100 men present and C. B. Murray as chairman. This was a round table discussion of iron ore beneficiation and of its relation to blast-furnace operations, and only one paper was presented, by Clyde E. Williams. Mr. Williams discussed the future of the Lake Superior district in its relation to the iron and steel industry. He stated that although estimates had shown that the total life of the present known iron ore reserves of the Lake Superior district was 20 to 30 years and that many believed that as a result of this depletion foreign ores would be brought to the Atlantic Seaboard, thus causing a displacement of the steel industry to the East, he believed that the Lake Superior district would continue to be the important producer of iron ore used in this country for decades beyond the predicted time before the exhaustion of the present known reserves. He described the three general types of ores that required concentration and pointed out the needs for research and the proper methods to be used in processes for the beneficiation of these low-grade materials. He discussed the effects of fine concentrates and the use of agglomerated ores in the blast furnace. This general summary led to interesting and valuable discussion on the various economic, ore-dressing, and blast-furnace problems in large-scale development of beneficiation. Perry Harrison described recent developments in sintering and the properties of iron ore sinter. T. B. Counselman and W. H. Coghill discussed the merits of classification of iron ore previous to tabling. Robert Faulkner and J. E. Little described the beneficiation plant of the Bethlehem Steel Corporation.

Jan 1, 1931

By H. N. Treaftis, J. W. Cahn

THE previous determinations of the solvus of tin in solid lead disagree with one another by as much as 40°C or almost 10 at. pct. Even determinations that appear to be careful differ considerably in both the solubility and its temperature coefficient. Recent kinetic workl -3 on the rate of precipitation of tin from lead-tin alloys and thermodynamic work4 on the heat of solution of tin in lead have given some insight into the time necessary to reach equilibrium in this system. As this time is longer than that used in almost all previous determinations of the solvus, these determinations are questionable. Since the interpretation of recent kinetic results requires accurate values of the equilibrium solubility the present work was undertaken. DISCUSSION OF PREVIOUS RESULTS The methods used in previous studies may be placed into three classes: 1) Several alloys covering a range of compositions are allowed to reach "equilibrium" at a certain temperature.5-7 Some property, such as the X-ray lattice parameter of the lead-rich phase or the re- sistivity of the alloy, is then measured as a function of composition. The solubility limit for that temperature is taken to be that composition at which a discontinuity in the property occurs. However, the recent kinetic work has shown that tin precipitates in two stages. The first stage is rapid but leaves the lead still supersaturated. The second stage is very slow, and it seems from the equilibration times quoted by the investigators of the solvus that the end of the first stage of precipitation was usually mistaken for equilibrium. This is especially true at temperatures below 100°C where the first reaction is still quite rapid (from minutes to months), but where the second stage is so slow that very long holding times are required to reach equilibrium. Alternatively micrographic work8 on several alloys of different compositions seems to have given good results if done carefully. 2) The beginning of precipitation in a homogenized alloy is measured as it cools slowly8-10. Since reactions in solids undercool easily, such determinations will always give too low a temperature for the solvus. 3) Some property of an alloy is measured as a function of temperature while the alloy is above the solvus.5,9,11 The range of temperature can usually be extended slightly into the two phase region. Then the alloy is precipitated at a much lower temperature and slowly reheated. The solvus is taken to be the lowest temperature where the property of the reheated alloy is equal to that previously determined for the homogeneous alloy. Usually one also expects a discontinuity at the solvus in the temperature variation of the property for the reheated alloy. The difficulty in this method is the sluggishness of the dissolution process, and this method may give too high a solvus temperature. EXPERIMENTAL The phase boundary or solvus temperature was determined by a modification of method 3 for a series of chemically analyzed high-purity alloys, ranging from 5.1 to 26.4 at. pct Sn. The resistance, as a function of temperature, of a sample of homogenized alloy (which could easily be undercooled) was compared with the equilibrium resistance which that alloy sample attained after precipitation at room temperature followed by long isothermal anneals at various temperatures. Before each anneal the sample was rehomogenized and reprecipitated. The solvus temperature could be located to within 1°C as the intersection of the resistance vs temperature curves for the homogenized and equilibrium alloys. No attempt was made to locate the phase boundary more accurately since the limiting factor was the precision with which the alloys could be analyzed. This precision was ±0.1 wt pct Sn and corresponds to an error of 1 deg in temperature. This use of isothermal anneals differs from some of the previous investigations in which method 3 was used with baths of slowly rising temperatures. It was found early in the investigation that solvus temperatures tended to be high if the latter method was used even at extremely slow heating rates. For example a

Jan 1, 1961

By V. V. Clark

WHEN a district is more or less primitive, and a trained mining engineer attempts single- handed to prospect it according to old standards, he generally fails. He has not the ability to live out in the open alone for months at a time and carry on with enthusiasm and determination like the old-time prospector. But the same engineer, placed in an organized group where modern prospecting methods are employed, is immediately put on his mettle and his chances of winning are greatly increased. Marsman Investments, Ltd., with headquarters in Manila, has at the present time, Sept. 4, 1937, six prospecting parties in the Netherland East Indies. Three of these groups are combing their assignments for lode mines, studying structures, developing and reaching out into veins and zones with diamond drills. The other three are searching for placer mines with pans, pits, and Empire drills. I am in charge of one group seeking commercial gold placers on the Island of

Jan 1, 1937

By C. M. Moncrief, B C. Craft

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By C. M. Moncrief

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946