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IRON AND STEEL COMMITTEE ALBERT SAUVEUR, Chairman .A. A. STEVENSON, Vice-Chairman HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Cambridge, Mass. Guilliaem Aertsen, Robert W. Hunt, .-E: Gybbon Spilsbury, John Birkinbine, J. E. Johnson, Jr., J. S. Unger, William H. Blauvelt, William Kelly, Felix A. Vogel, Charles A. Buck, Charles Kirchhoff, Leonard Waldo, James Gayley, Richard Moldenke, William R. Walker, Henry D. Hibbard, Joseph W. Richards, William R. Webster, Henry M. Howe, C. F. W. Rys, Frederick W. Wood. Manuscripts of the following papers on iron and steel for the February -meeting have been received and accepted: Albert Sauveur, Notes on Heating and Cooling Curves of Professor Carpenter's Electrolytic Iron. H. M. Howe and A. G. Levy, Notes; on the Plastic Deformation of Steel during Overstrain.

Jan 2, 1914

By Thomas F. Donnelly

Discussion of the paper of THOMAS F. DONNELLY, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1759 to 1768. F. LYNWOOD GARRISON, Philadelphia, Pa. (communication to the Secretary *).-The paper is of value in giving the public some first-hand information regarding a copper property that from various causes has attracted considerable attention, especially in Philadelphia, and which has also been the source of several fantastic flotations that had little to recommend them. Since 1906, no work has been done on this property under my direction, with the exception of a topographic survey made last winter by Mr. Donnelly, which was intended as the first step in a sound and logical system of development. From 1906 to 1915, desultory attempts were made to develop these orebodies, but as the work was not in competent hands much money was wasted and even more disappeared in ways regarding which it is perhaps not best to inquire. The result is, this interesting property has now practically no more ore developed upon it than in 1906, despite the fact that a new 100-ton mill is being erected, although, as I have intimated, it is today not much more than a prospect. Turning now to the scientific and more agreeable side of the subject, it is interesting to note that these Santo Domingo copper ores are invariably found in volcanic tuffs and that, in a geologic sense, they are all very old, for there are no evidences of recent volcanic activity in the greater Antilles, of which this island is the second largest. The existence of copper in tuffs in different parts of the world is a notable fact. Often, if not usually, it is present in mere traces, but not infrequently we find it in sufficient amount to be of economic importance. Thus, for example, chalcopyrite and bornite occur in the Tertiary tuffs of Japan, and a number of producing copper mines of that country are either actually in, or closely associated with, rocks of this character. Whether the copper minerals are original primary ores in the tuffs, or were derived from accompanying eruptive dikes, appears not yet to have been determined in any instance. In most of the Japanese cases of which I can find any record the tuffs appear to be associated with shales and limestones. These Japanese copper ores also carry some gold, especially in the upper parts of the veins; in this they resemble the Santo Domingo deposits which not infrequently carry as much as $6 or $7 per ton of gold on the outcrop. As a rule the content of gold in both the Japanese and

Jan 12, 1915

By A. W. Ambrose

The underground losses of oil exceed by hundreds of thousands of barrels all the oil that has been lost in storage, transportation, or refining. The quantity lost is, of course, indeterminate; but when it is considered that the contents of an entire oil field have been excluded from recovery by invading waters, some idea of the amount wasted may be gained. Similarly, enormous quantities of gas have been lost underground. Conservation of the oil, therefore, should start before it is brought to the surface rather than after it is placed in storage tanks. Water is one of the most important causes for underground losses and the operator should give as serious consideration to an underground flood of water as he would to a destructive surface flood. The best insurance, of course, is to have the wells drilled in such a manner that water has no access to the productive oil and gas horizons, and on abandonment the wells should be properly plugged. The encroachment of edge water and the occurrence of waterin;the base of an oil sand present a very serious problem to an oil company sooner or later these waters are bound to cause considerable damage, if they do not entirely destroy the possibilities of further production. Too often, however, a field has been considered to be in a hopeless condition, whereas wells in as bad a condition in other areas have been repaired and the life of the field appreciably lengthened. The corrections are very often suggested by technical study. Very successful results have been accomplished by detailed underground work in the California oil fields, in Cushing, Oklahoma, and in other areas. The purpose of this paper is to outline briefly1 general methods of analyzing oil-field water problems in a producing or in a producing and developing oil field, with a view to suggesting repair work on offending wells. Reference is continually made to producing oil wells; the same general method of procedure, however, should be adopted in a gas field.

Jan 1, 1921

Following is the personnel of the various society and national committees on which the A I M E is officially represented United Engineering Society Officers of the Board, 1921 JOHN VIPOND DAVIES, President CALVERT TOWNLEY, 1st Vice-president ALFRED D FLINN, Secretary WILLIAM L SAUNDERS, 2d Vice-president JOSEPH STRUTHERS, Treasurer Finance Committee House Committee CALVERT TOWNLEY, Chairman ALFRED D FLINN, Chairman GEORGE H PEGRAM . H S CROCKER WILLIAM L SAUNDERS BRADLEY STOUGHTON GEORGE M BASFORD CALVIN W RICE F L HUTCHINSON

Jan 1, 1923

By A. E. Wells, H. O. Hofman, R. P. Reynolds

A Discussion of the Paper of H. O. Hofman, R. P. Reynolds and A. E. Wells, read by title at the London Meeting, July, 1906 ; presented at the New York Meeting, April, 1907, and printed in Bi-Monthly Bulletin, No. 13, January, 1907, pp. 37 to 52. GEORGE A. PACKARD, Boston, Mass. (communication to the Secretary*) :-The very interesting results obtained by Prof. Hofman and his assistants came to my attention when I had temporarily assumed charge of the metallurgical department of the Missouri School of Mines, and had found it, pending the completion of a new building, lacking a furnace in which to roast ore preparatory to the customary lead blast-furnace run. An attempt at lime-roasting had been already determined upon, but the use of a charge which would make a slag of definite composition was a new idea. The results following were obtained by Messrs. Aubrey Fellows, J. C. Long, E. R. Wash, and Dr. T. C. Tseung, under my supervision. It is regretted that the data are not more complete; but the work was done simply incidentally to securing the desired ore for the blast-furnace, with no idea of obtaining any results of especial interest. It is submitted because of the metallic lead obtained, no notice of which has been seen elsewhere. The ore was an aggregate of several lots of concentrates, apparently from Missouri ores. The analysis follows, with that of the limestone and sandstone used, as far as made:. Ore, SiO2, 3.04; Fe, 0.77; CaO, 2.53; Pb, 68.74; Zn, 5.77; S, 13.9 per cent.; limestone, SiO2, 1.0 ; CaO, 54.35 per cent.; sandstone, SiO2, 99.8 per cent. The converter was made in the shops from a sheet of No. 14 iron riveted in the shape of a truncated cone, 20 in. in diameter at the top, 15 in. at the bottom and 22 in. high. A grate of No. 8 iron, 17 in. in diameter, with 130 s-in. holes placed at about 1.25-in. centers, was held in place by the shape of the

Jul 1, 1907

By LEE H. CORNELL

Drilling activity in Kansas during 1945 continued at an accelerated pace to meet the demands of war; 1810 tests were drilled as compared with 1856 tests the previous year, 1771 tests in 1943, and 1516 tests in 1942. During the year 31 new oil pools and 10 new gas pools were discovered. Of a total of 364 wildcats drilled, 323 were dry; and of 1446 tests drilled in pools, 825 were oil wells, 197 gas wells, and 425 dry holes.

Jan 1, 1946

By J. Warner, M. J. Marcinkowski, B. Cullen, T. Prevender, J. Mcllwain, T. Carnahan, J. Pahlman, J. Demel, J. Munford

The following analysis was an outgrowth of a midterm examination given by one of the authors (M.J.M) in a course entitled Metallurgy 541 "Applications of Dislocation Theory'' at Iowa State University. Fig, l(a) shows the three-layer sequence of atoms lying in the (111) plane which characterizes the fully ordered AB3 fcc crystal, i.e., LI2 type. If any two-layer sequence of close-packed planes is constructed from Fig. 16)' the structure would be hcp of the DO,, type. Consider for convenience that the circled atoms lie in the plane of the drawing while those shown square and triangular lie immediately above and below the plane of the drawing, respectively. It has already been shown' that if a Shockley partial dislocation is passed over the plane of the paper, then the square atoms in Fig. 1(a) are displaced from their original positions as shown by the arrows in Fig. l(b). Not only is an intrinsic fault produced but the crystal is simultaneously disordered across the slip plane. In particular, 2AB bonds are converted to 1AA and 1BB bonds when referred to the area outlined by the solid line in Fig. 1. If, on the other hand, a Shockley partial is allowed to pass immediately above and immediately below the plane of the paper so as to displace the atoms in opposite directions as shown in Fig. l(c), an extrinsic fault is producedZ and twice the amount of disorder is introduced into the crystal as compared to the dislocation-produced intrinsic fault, if only broken first-neighbor bonds are counted. If an intrinsic stacking fault is produced by removing a close-packed plane of atoms in Fig. l(a) and displacing the two adjacent planes by 1/3a0[111], no wrong nearest-neighbor bonds are produced. Similarly, if an extra half plane of atoms with the same arrangement as any of those shown in Fig. l(a) is inserted between any two planes in the same figure, then an extrinsic stacking fault is produced in which once again no wrong nearest-neighbor bonds are produced. The latter two faults are bounded by Frank partial dislocations. Since, at least in the alloy CU3AU,3 nearly all of the ordering energy resides in the first nearest-neighbor interactions, intrinsic and extrinsic stacking faults and associated APB's of the Frank type are expected to have significantly lower energy than those of the Shockley type in CusAu in particular and quite likely in L1, and DO19 type alloys in general. Also, because of the higher degree of disorder plus loop interaction

Jan 1, 1968

By John K. Hammes, Stanley D. Michaelson

Generally, the mining costs reported for the large open-pit operations in the United States and South America lie within the range of $0.20 to $0.30 per ton of material moved. (These operations have strip- ping ratios ranging from 1.5 to 4.0.) Productivities for the larger North American properties are in excess of 200 tons of material per man shift, while those for the South American operations are less than 200 tons per man shift. The most significant variations in cost are in the categories of haulage and general mine cost. Haulage costs vary, as expected, according to the mine elevation, pit profile, crusher location, and accessibility of a dump area, and general cost variations depend largely on the overhead cost items included in this category. Drilling and Blasting Practice The majority of open-pit copper mine production drilling is performed by rotary drills. Hole diameter varies from 6 in. to 12 in., with 9-in. holes being most common, and penetration rates vary from 35 ft to 60 ft per hour.

Jan 1, 1968

By M. A. Jones

Performance of a pilot flood in eastern Kansas indicates improved recovery and accelerated production resulting from mobility ratio control obtained by adding a high moleculur weight polymer to injected water. Ultimate pilot flood recovery of the 75-cp reservoir oil is anticipated to he 350 bbllacre-ft during the six-year flood life. Cumulative recovery to date totals 242 bbl/acre-ft after 30 months of injection. Reservoir parameters and flood performance are disc~rssed in detail to provide a case history relating to the feasibility of polymer flooding. INTRODUCTION The Vernon Polymer flood of the Brazos Oil & Gas Co., located in Sec. 2, 24 S., 16 E., Woodson County, Kans., was begun in late Oct., 1963. Injection of a 500 ppm solution of Pusher* polymer was initiated in a 15-acre pilot to determine feasibility of improving oil recovery by mobility ratio control. Performance to date and the anticipated recovery of 115,000 bbl from the 329 acre-ft pilot indicate efficient displacement of the viscous reservoir oil. Dependence of flood recovery on the displacing fluid-displaced oil mobility ratio has long been recognized. Displacement efficiency of the reservoir oil decreases with increasing mobility ratio. Therefore, economic reduction of this parameter is an attractive approach to improving oil recovery. particularly from viscous oil reservoirs where mobility ratios are often quite high. Waterflood mobility ratios can be controlled by dilute solutions of certain polymers'; which provide a displacing fluid with considerably reduced mobility. Reservoir parameters and flood performance are emphasized in this paper to provide data relating to polymer flood applicability. THEORY The polymer used in the Vernon pilot exhibits the property of unusually high resistance to flow through porous media.'.' A small concentration in injected water effects a mobility reduction considerably beyond that predicted from increases in bulk viscosity as measured in a capillary or rotating cup viscosimeter. Water mobility in the subject flood is reduced by a factor of 7.55 with the addition of 500 ppm Pusher chemical to injected water while the bulk viscosity is increased from 1.03 to only 1.40 cp at 75F. The exact flow mechanism causing resistance to flow has not been established; however, it is observed only in tortuous flow systems and appears to be influenced by brine properties, rock properties and oil saturation. Consequently, mobility reduction is estimated from flow studies for a given sample of reservoir rock and is expressed in terms of a "resistance factor".' This parameter is defined as the ratio of brine mobility to polymer solution mobility measured at residual oil saturation: RF= ?m/?p= (km/µm)/(kp/µp)M.......(1) where RF = resistance factor (dimensionless) k*. and A, = mobility of water and polymer solution, respectively k,,, and k,, = water and polymer permeability, respectively (darcies) µie and µp = viscosity of water and polymer, respectively (poise). Eq. 1 is similar to the expression commonly used to relate the relative mobility of the water bank at residual oil saturation to oil-bank mobility at irreducible water saturation: where M =mobility ratio of water to oil (dimension-less) A, = mobility of oil k, = permeability to oil (darcies) )i* = oil viscosity (poise). From Eqs. 1 and 2 it is apparent that the polymer-solution-to-oil-mobility ratio can be approximated by dividing the brine-to-oil ratio by the resistance factor RF: Mpn=M10/RF...........(3) where M,-, = mobility ratio of polymer solution to oil (dimensionless). This simplified presentation assumes no dilution of the polymer solution by connate water. Also, the presence of a connate water bank separating the polymer solution from the displaced oil is not considered. Displacement of oil by waterflooding is increasingly dominated by viscous forces as the viscosity of the oil displaced increases. When the oil mobility is less than that of the injected water, the oil-water interface is not a piston-like front.3,' Instead, instabilities occur at the flood front in the form of viscous fingers which tend to penetrate the less mobile oil bank. The magnitude of these protrusions, or the degree of channeling, increases

Jan 1, 1967

By R. Priestner, R. F. Krause

Solid, cylindrical crystals of a iron have been fractured at 10°K by the simultaneous application of tension and torsion stresses. Thus, a complex distribution of normal (sN) and shear (ss) stresses existed in a cleavage plane at fracture. In every crystal the clearage-plane normal was inclined to the specimen axis, so that a unique point, M*, in the operative cleavage plane was defined where the quantities sn and s2 N + s2 S) were maximized. It is shown that the maxirrzum resolved normal stress on the cleavage plane at fracture decreased as the resolved shear stress in the cleavage plane at M* increased. Thus, a normal stress la?*! for fracture was not satisfied. A fracture law which takes shear stress into account. and which predicts that (s2 N +s2S) should be constant, is to be preferred. However, the data is best represented by a linear dependence of sN on sS, sS which 110 physical significance can be attached. It is suggested that the fracture-nucleating -mechanism is a short-range one. A critical stress law has not yet been unequivocally established for the propagation of cracks in metals. Measurements of the tensile fracture stresses of variously oriented zinc single crystals1 failed to establish the normal stress law expressed by In Eq. [1], sN is the fracture stress, P, resolved normal to the fracture plane, and 0 is the angle between the fracture -plane normal and the stress axis. Similarly, a comprehensive investigation failed to verify the normal stress law for the tensile fracture of a-iron single crystals.' However, a subsequent investigation,3 using iron from the same ingot, presented fracture data which obeyed the normal stress law. It has been shown previously4,5 that the Griffith criterion for fracture6 does not predict such a normal stress law. This result is of particular significance in considering the fracture of metals, such as zinc and iron, which may fail by cleavage. In these metals fracture propagates in a well-defined "cleavage" plane, whether or not an applied stress is normal to it. When the cleavage-plane normal deviates from the direction of application of a uniaxial stress, for example, the crack propagates under the combined action of normal (sN) and shear (ss) stresses. When the presence of a resolved shear stress in the crack plane is taken into account, the Griffith criterion is expressed by4

Jan 1, 1967

By George E. Beavers

Under the title used for this paper, the converter practice of the Tennessee Copper Co. is described in the TRansactions of the Institute.l That article contains the following statement: "The limit in capacity of the Peirce-Smith converter in terms of concentrate has not been reached but approximately as high as one ton of concentrate has been handled for each ton of liquid matte charged and good working conditions have been maintained." It is not the intention of the writer to review the conditions leading up to the introduction of a Peirce-Smith converter at Copperhill, but, instead, to offer later data to show how satisfactory the installation has been. Converter Campaign, June 15, 1930 to August 23, 1931 Blowing time (converter days)............... 349.90 Number of blows........................... 427.00 Tons matte charged........................ 38,335.00 Copper assay of matte, per cent.............. 13.67 Tons blister copper made.................... 9,246.00 Time to blow one ton of copper, minutes...... 54.50 Air used per minute, cu. ft................... 12,500.00 Blast pressure, lb........................... 12.80 Air per ton copper, cu. ft.................... 681,330.00 Air per ton iron, cu. ft....................... 199,040.00 Tons flux used............................. 11,845.00 Tons flux per ton matte..................... 0.31 Tons flux per ton copper.................... 1.28 Tons flux per ton iron....................... 0.37 Tons concentrate treated.................... 28,960.00 Copper assay of concentrate, per cent......... 17.13 Tons concentrate per ton matte.............. 0.76 Tons material charged per converter day...... 235.70

Jan 1, 1934

By D. L. Kelley

High-viscosity water injection has been proposed for use in reservoirs containing high-viscosity crude oils. Previous publications have largely ignored the possible effects of the connate water on the proposed process. This paper describes experimental work which indicates that the connate water will be forced ahead of the injected water to form a bank of low-viscosity water. This decreases the oil recovery which would be expected if such a bank were not formed. These effects are shown for a range of fluid mobilities and connate-water saturations for a five-spot injection system. In general, oil recoveries using viscous water are significantly greater than for untreated water even though they are less than would be expected if no connate water bank were formed. INTRODUCTION The effect of mobility ratio on the oil recovery of wa-terfloods has been known for many years. Muskat first pointed out that the fluid mobilities (k/µ) in the oil and water regions would affect the performance of the water-flood, and he estimated the general effect of these variables.' Since this early work, studies of the effect of mobility ratio on secondary recovery have been reported where mathematical,' potentiometric3 and scaled flow models' were used. These studies have shown that a reduction in the mobility ratio between the oil and the displacing fluid would cause additional oil recovery when water-flooding reservoirs containing viscous crude oils. Studies reported by Pye- nd Sandiford 8 have indicated that chemicals to increase injection water viscosity are now available and can be used to reduce the over-all mobility ratio of a waterflood. Where mobility ratios are controlled by the injection of viscous fluids, the connate water of the reservoir can play an important part in the displacement of the reservoir oil. The purpose of this study was to determine the effect of the connate-water saturation in waterfloods where viscous waters are used for injection. DISPLACEMENT OF THE CONNATE WATER Russell, Morgan and Muskat7 were the first to recognize the mobility of connate waters in waterflooding. They conducted waterfloods on oil-saturated cores containing 20 and 35 per cent irreducible water saturations, and found that from 80 to 90 per cent of the "irreducible" water was produced after only one pore volume of water was injected. However, their experiments were conducted at rates of flow significantly higher than those ordinarily occurring in waterfloods. Also, the cores were only from 4.0 to 8.5 cm long. Brown 4 studied a 100-cm linear sand pack which had been prepared to contain connate water and oil. He used 140- and 1.8-cp oils with injection water of essentially the same viscosity as the connate water. He found that all of the connate water was displaced by the injection water in both cases. However, the injection volumes required for complete displacement of the connate water were considerably higher in the case of the more viscous oil. To verify the results of the foregoing experiment, a 10-ft-long linear model was constructed by packing 250-300 mesh sand in a 1/2-in. diameter nylon tube. The model was evacuated, saturated with a brine of 1-cp viscosity, and flooded with a 41-cp mineral oil to the irreducible water saturation of 10.9 per cent. The model was then waterflooded by the injection of a water solution which had an apparent viscosity of 42.6 cp. The solution consisted of 0.5 per cent methylcellulose in distilled water. The viscosities of the oil and connate water were measured with an Ostwald viscosimeter. The viscosity of the polymer solution was calculated by Darcy's law using pressures measured during actual flow conditions. The ratio of the mobility in the oil region to the mobility in the inject ion-water region was approximately 0.32. The mobility ratio of the oil region to the connate-water bank was approximately 14. The mobility ratio between the connate-water bank and the injection water region was 0.024. Approximately 84.5 per cent of the recoverable oil was produced before water breakthrough. Immediately following breakthrough, oil and connate water were produced at an increasing water-oil ratio until the viscous injection water broke through. At viscous-water breakthrough, 96 per cent of the original connate water had been produced. After breakthrough of the viscous water, there was no additional production of connate water or oil. The near-

Jan 1, 1967

[United Engineering Trustees, Inc. ALBERT ROBERTS. '47 R. M. ROOSEVELT, '49 RALPH B. WILLIAMS, '48 The Engineering Foundation F. F. COLCORD. '46 M. A. PRENTIS. Jn.. '48 It. >I. ROOSEVELT. '49]

Jan 1, 1946

By Henry Carlisle

Henry Carlisle: This is November, 1960, and my good friend John Gustafson is sitting on the other side of a tape recorder. I, Henry Carlisle, am going to ask him some questions on the highlights of his life, and he has been good enough to say that he will play this question and answer game with me. Now, John, let's pick out a very interesting period when you went to North Labrador and made a preliminary investigation of the big iron deposits there. You were working for either Timmins or Hollinger, which was it? John K. Gustafson: I was in charge at that time of a Hollinger Exploration Co. office in Toronto. We had acquired options on enough shares to control Labrador Mining and Explorations Co., and through Hollinger North Shore Ltd., another company, we had a 3000 square mile concession in Ungava, Quebec, on the direct extension of the iron ore fields.

Jan 7, 1972

By R. P. Abendroth

This study is concerned with the kinetics of selective oxidation of chromium in a commercial Fe-Cr-Ni alloy. Selective oxidation of chromium in this alloy, by use of a low oxygen-potential atmosphere, leads to the formation of a compact, protective layer of Cr2O3. This layer serves to protect this alloy from gross scaling when it is subsequently exposed to severe oxidizing conditions at high temperature. The interaction of low oxygen-potential atmospheres close to equilibrium with Fe-Cr and Ni-Cr alloys has been studied by others."' These studies werk concerned with the surface-structure variations under slightly oxidizing conditions. NO detailed study was made of the oxide scale formation kinetics, however. The alloy samples were cut from 0.012-in.-thick sheet, with an apparent surface area of 7.1 sq cm. These sheet samples were abraded through 4/0 metallographic paper, and washed in alcohol and acetone. The analysis of the sheet alloy is (in weight percent): 42 pct Ni, 5.5 pct Cr, 0.09 pct C, 0.18 pct Al, 0.36 pct Si, 0.26 pct Mn, balance Fe. The weight gain vs time data were obtained with a 2-g capacity fused-silica spring—cathetometer system. The spring deflection was optically magnified ten times before being read by the cathetometer. A sensitivity of about 0.01 mg was attainable. The spring was enclosed in a water jacket maintained at 60°C to minimize the effect of temperature changes. The sample was suspended from the spring with a fused-silica hangdown and was positioned in the thermal center of a mullite furnace tube. Sample temperature was read with the aid of a thermocouple placed outside the mullite tube and an inside vs outside temperature calibration. Temperature change during the course of a run was ±0.25°C, with a temperature gradient of less than l.O°C over the length of the sample. Total temperature uncertainty was no more than ±3.0°C. Alignment difficulties between the hangdown and radiation shields in the furnace tube required that the sample be positioned in the furnace when cold, and heated with the furnace until the temperature stabilized at the desired point. This required 5 to 6 hr, and was carried out in Matheson ultrahigh-purity hydrogen. Oxidation was started, after evacuation, by introducing a hydrogen-water vapor mixture, obtained by saturating hydrogen with water vapor at 31.00o ± 0.02oC. Oxidation was continued for 90 min. Gas flow was 300 ml per min during heat up and oxidation. Since only several milligrams of oxide are formed on each sample, chemical analysis of the oxide is difficult. A representative analysis is: 80 pct Cr2O3, 5 pct Fe2O3, 3 pct Al2O3, 4 pct MnO, 7 pct SiO2, 1 pct or less NiO. X-ray diffraction analysis of the oxide as formed on the alloy gives rhombohedra1 Cr2O3, and barely distinguishable amounts of a cubic spinel phase, and possibly AlZOs and SO2. The identification of these latter two compounds is by no means certain. The spinel phase could be based on iron or manganese as these elements are present in significant amounts in the oxide. The results of the kinetic studies using 31°C dew-point hydrogen-water vapor mixtures were found to conform to a parabolic rate law. In many cases the parabolic plot consisted of two intersecting straight lines, defining an early and a late rate for a particular run, and in the other cases the parabolic plot consisted of one straight line for the entire run. The slopes of the various straight lines were determined by the method of least squares. Reproducibility of the data was good enough for multiple runs at the same temperature such that the value given for the rate constant is the average for two or more closely similar values, rather than widely varying values of the rate, where more than one determination is indicated in Table I. The exhibition of only one or of two rate constants during a run can happen at the same temperature. Thus, Table I shows that at 11'74°C a single rate constant was obtained from one sample, while other samples oxidized at the same temperature gave an early and a late rate constant. It should be noted that the single rate constant corresponds very closely with the early rate constant. This is also true at 1153°C. The time at which the late rate started to appear was variable, usually occurring 20 to 40 min after oxidation had started.

Jan 1, 1964

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.' The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750' and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By R. C. Hirschfeld, H. H. Einstein, R. W. Bruhn, R. A. Nelson

The objective of the model studies described in this paper is to determine the effect of planar discontinuities on the strength and deformability of a rock mass. A model material was used because it satisfied concurrently three requirements that available natural-rock samples did not: (1) low strength, which was desirable for minimizing the loads that had to be applied in the laboratory; (2) ease of producing test specimens with geometrically regular joint patterns; and (3) uniformity of the test specimens. The model tests were performed on specimens made from a single modeling material and tested under triaxial stress conditions with [u,=u,]. Results are presented in this paper for tests on specimens that had (1) a single joint set inclined at several angles to the major principal direction, including 0º and 90°, and (2) two joint sets that were mutually perpendicular, one set perpendicular to and one set parallel to the major principal direction. Several different joint spacings were used in each series. Future tests will include a series with two sets of joints that make oblique angles with each other and with the major principal direction. The results of model tests and tests on cores of jointed rock by several investigators (e.g., Müller and Pacher,l Moore,2 Krsmanovic and Milic,3 Hayashi,4 Rosenblad,5 Jaeger,6 and Lane and Heck 7, have contributed significantly to the design of these experiments, which are believed to be the first in which a comprehensive study has been made of the combined effects under triaxial loading of joint spacing and joint orientation (Fig. 1).

Jan 1, 1970

By C. W. Lawr

The ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, arc mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 Ib.) KCN per ton of solution. As the daily discharge to the dam was 1600 tons' of slime of a 2:1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and it's recovery held alluring possibilities. Principle of Cyanide-recovery Process As it had acquired the patent rights to theLayng (H. R.) and Halvor-sen (A. L.) processes, also those of Mills (L. D.) and Crowe (T. B.) after considerable experimental work in its own laboratory and at Tonopah, Nev., The Merrill Company of San Francisco early in 1923 notified the Mexican Corporation and compania de Santa Gertrudis of its process for the recovery of cyanide from weak wash solutions, or for the transference of cyanide from a foul mill solution to a clean alkaline solution. This method is known as the Mills-Crowe process, the principle of which is as follows: The solution from which the cyanidc is to be removed is made acid by bringing it into contact with sulfur dioxide (SO2). The acidified solution is the; transferred to a closed tank in which air and solution are brought into intimate contact. The air leaving the tank charged with HCN is then passed to another tank in which it is mixed with an alkaline solution,

Jan 1, 1930

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970