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By W. J. Joslin

The frontal-advance equation can determine how the fluid withdrawal rate and subsurface operating pressure influence oil recovery from pressure-maintained reservoirs having characteristics favorable for efficient vertical segregation. For effective vertical segregation in formations having low dip angles, the requirements are: thick, massive sands, low viscosity oil and high vertical permeability with few discontinuous shale members. This approach has been successfully applied to the LL-370, which is a massive Eocene sandstone reservoir containing crude with an average gravity of 26" APT, a dip of only 3" and vertical permeability of ½ darcy. The average gas cap saturation was calculated for various rates of vertical gas-oil contact movement corresponding to a wide range of reservoir producing rates. This method also evaluated the effect of different pressure maintenance levels on oil recovery. Applicability of this procedure for calculating the present oil saturation in the LL-370 gas cap has been substantiated from field performance, where the oil saturation was computed by comparing oil recovery with the gas cap volume vacated. INTRODUCTION During the natural depletion history of the LL-370 reservoir, located in Lake Maracaibo, Venezuela, excellent vertical segregation resulted in the formation of a thin gas zone over a substantial portion of the oil-productive area. Subsequently, gas injection forced this thin gas-saturated zone slowly downward, reducing the oil saturation in the gas cap to a low value. The oil recovery has been raised considerably above earlier predictions where vertical segregation effects were under-estimated. In order to determine the maximum efficient producing rate and optimum operating pressure for this reservoir, a vertical gas frontal-advance analysis has been made through application of the fractional flow equation. LL-370 RESERVOIR CHARACTERISTICS The reservoir consists of a truncated monocline of massive. highly-permeable Eocene sandstone, called the B-b formation, covering an area of more than 13,500 acres. The original oil in place was 2.17 billion STB. Internal non-sealing faults subdivide the structure into four blocks called the B-6-x.6, 10, 11 and 13, which are effectively bounded by major faulting on the flanks, an unconformity updip to the west, and an immobile aquifer to the southeast. The producing formation occurs at an average depth of 5,250 ft subsea and has a closure of more than 1,500 ft. A typical producing section has a net oil sand thickness of 170 ft. Scattered throughout the section are a few randomly-positioned shale lenses which increase in thickness and areal extent downdip. The reservoir rock and fluid properties vary with depth. The permeability and produced oil gravity are 1600 md and 28" API at the top, compared to 300 md and 18° API at the water-oil contact. The productivity of updip wells is, therefore, much higher than the reservoir average. The reservoir oil was originally saturated at the crest, grading to a slight degree of undersaturation at the water-oil contact. There was no original gas cap; and material balance and the field performance indicate no water influx. Except for the northern B-6-x.6 block, the fluid and rock properties have already been published.' Average LL-370 reservoir properties are shown in Table 1. RESERVOIR PERFORMANCE UNDER NATURAL DEPLETION Fig. 1 shows production performance from 1939 to date. Early development was gradual, with 30 wells pro-

Jan 1, 1965

By Joachim J. Hauser

William F. Hosford, Jr. (Massachusetts Institute of Technology)—Dr. Hauser has used a very interesting method to study the interaction of dislocations on different slip systems, but it should be pointed out that the analysis of the experiments is subject to a serious criticism. He states that "the effect of the compression can be adequately described by one slip system." The effect of frictional constraint during the compression makes this quite unlikely. When a block of metal is compressed its lateral expansion requires a sliding of the metal over the compression platens. The role of friction in the interface between the deforming metal and the platens is to increase the normal force required for the compression. Analyses1213 have shown that, in general, the additional force, p, required for the compression is a function of l/h where is the coefficient of friction, I is the length of the speci- men in contact with the platens. For a constant COefficient of friction, isho' shows that P should increase exponentially with pl/h for both plane strain and axially symmetric compression. For a compression specimen, Fig. 7, whose cross section perpendicular to the compression axis is a rectangle whith one dimension L, much larger than the other W, a much larger force would be required for appreciable flow parallel to L than for flow parallel to U7. Therefore lateral strain in the W direction, EW, should be much greater than the lateral strain in the L direction EL. Since L/H = 14.5 for Dr. Hauser's crystals, and since no lubrication was used, it seems questionable that appreciable lengthening of the crystals could occur. Because the theories of frictional constraint have been derived for isotropic polycrystalline materials, it was decided to make experimental measurements on a single crystal. A section 3.590 in. long was sawed from an aluminum single crystal with a square section of 0.249 in., so that L/W= 14.4. This crystal was tested in compression between dry ground steel platens. Fig. 8 shows the orientation of the crystal and the axis of compression. The face for compression was chosen so that the operation of the single-slip system which would be predicted in the absence of friction would lead to a larger strain in the length direction than in the width direction. The dimensional changes of the width and length as well as the height were measured frequently during the compression with micrometers. Width strains were calculated from the average of readings near each end and at the center. A plot of the length strain, EL, against the width strain E w is given in Fig. 9. The slope indicates that the EL amounted to only 2.5 pct of cw. Other compression tests on similar crystals with shorter lengths also showed severely limited elongation. Even for a crystal with L/W = A.0, EL was only about 26 pct of cw. Because of the frequent interruptions of the tests for dimensional measurements should have decreased the frictional constraint by allowing a reseating of the platens, even smaller elongations under continuous testing seem probable. These tests on long narrow crystals show that essentially plane strain conditions prevailed. We may assume that Dr. Hauser's crystals deformed similarly. That the compression can be described by the

Jan 1, 1962

By C. Land, R. Hultgren

Heat contents of four Cr-Ni alloys were determined in a diphenyl ethev calorimeter. Aside from ferromagnetic effects, Kopp's law of additivity of heat capacities is approximately fol-lowed, in disagreement with earlier results of A. W. Foster. In 1934 Foster1 reported heat-capacity measurements of dilute solutions of chromium in nickel, primarily as a study of the effect of alloying on the ferromagnetic Curie temperature. He found that, apart from the Curie temperature effect, the general level of heat capacities was reduced 10 pct by the addition of 1 pct Cr; 20 pct by the addition of 2 pct Cr. His measurements of pure nickel essentially agreed with accepted values. These results indicate that small amounts of dissolved chromium cause an increase in the Debye temperature of nickel, presupposing a change of frequency of interatomic bonding vibrations which is much larger than should be expected. If Foster's results were verified, therefore, they would have important implications for bonding theory. The only other heat-capacity measurements in this system seem to be those of Taylor and Hinton,' who studied anomalies which they attributed to super-lattice formation at 25 at. pct Cr. At temperatures above the anomaly, Taylor and Hinton found heat capacities at this composition were quite normal, approximately obeying Kopp's law of additivity. EXPERIMENTAL WORK In order to verify or disprove the remarkable results of Foster, the heat contents of four dilute solid solutions of chromiunn in nickel were measured in a diphenyl ether calorimeter. This instrument, described elsewhere,, operates on the principle of the Bunsen ice calorimeter, but uses diphenyl ether as the working substance. Diphenyl ether melts at the convenient temperature of 26.S°C and supplies a more sensitive measure of heat than ice. The hot sample, in an atmosphere of argon, is dropped from a furnace at a measured temperature into a chamber which is surrounded by a mixture of solid and liquid diphenyl ether. The heat from the hot specimen melts some of the solid without chang- ing the temperature of the calorimeter. The amount of solid melted, and therefore the number of calories released by the specimen, is measured from the increase of volume of the mixture, which pushes mercury down a graduated capillary tube. The apparatus has been standardized against the known heat content of pure platinum. Heat loss during the dropping of the specimen was estimated by comparing the heat content of an empty platinum capsule with a solid platinum ball of the same radius and degree of polish of the surface. Repeated tests demonstrate the precision of measurement to be closer than *0.3 pct. Smoothed experimental results are listed in Table I. The tabulated values for pure nickel are taken from kelley, several measurements were made which agreed closely with this tabulation. For chromium, however, no similar agreement was found. The values tabulated were taken from a thorough study of chromium with the diphenyl ether calorimeter which will be published elsewhere.= Suitable plots of the data showed the expected ferromagnetic anomalies in the low-chromium alloys, while the 11 pct alloy shows no ferromagnetic anomaly, but a different, small anomaly below 900°K. This is perhaps the same anomaly found in CrNi, which was once attributed to superlattice formation,' but is probably due to some other cause, such as antifer-

Jan 1, 1960

By C. E. Shoenfelt

There was a notable decrease in drilling operations in 1940 in all of the Rocky Mountain states except Montana, where the two large fields on the Canadian border, Cut Bank and Kevin-Sunburst, were espe-cially active. The expanding markets for Montana natural gas made necessary the more intensive development of such fields as Rowdoin, Cedar Creek and Devon. While there were no important oil and gas discoveries in 1940 in any of the Rocky Mountain states, a few small pools were opened, which may constitute separate areas but may prove with later development to be extensions of old fields. Some of the old fields were extended and deeper pay zones were discovered in others. These have given the areas greatly increased oil reserves and therefore are just as important as the discovery of new fields. The more important of the developments in 1940 are given, by states, in the following paragraphs. Colorado Hiawatha Field, Moffat County.—The Mountain Fuel Supply Co. began the development at Hiawatha of its oil reserves, which were discovered in about 1929, and late in the summer oil began moving from the field by truck to the shipping point at Rock Springs, Wyoming. The Hiawatha field of northwestern Moffat County was discovered in 1927 by the Sormir Petroleum Co., with the completion of No. r Florence Wilson for 4,5,000,000 cu. ft. of gas a day from a Wasatch sand lens at 2200 it. In later development of the field, oil showings were reported in several wells but no development of this resource was undertaken until 1940, when a test of the oil possibilities was started with the release in April of a location for No. 5-A Wilson on the S\W. SW. NW. of sec. 23-1zN-1ooW., on the east side of the field. The Well had an initial production of 327 bbl. of oil a day pumping from three Wasatch (Tertiary) sands between 2005 and 2540 ft. It was drilled to 2562 ft., where the 65/8-in. casing was cemented and gun-perforated at 2005 to 2125 ft., 2260 to 2335 ft. and 2513 to 2540 ft. At the end of the year, this well was averaging zoo bbl. of oil per day, pumping. Two other wells were drilled for oil on Hiawatha during the summer—one a small well of 60 bbl. per day and the other a small gas well. Powder Wash Field, Moffat County.—The development of the Powder Wash field in northwestern Colorado was resumed in 1940 by the Mountain Fuel Supply Co., with the release of a location for No. 2-A Musser in the CWL.NW.SE. of sec. 4-1rN-97W. The Powder Wash field was discovered in 1931 by the Mountain Fuel Supply Co. and the discovery well, No. I Musser, on C.NW. of sec. 5-IIN-97W., was completed at 2152 ft. in the Hiawatha member of the nonmarine Wasatch for-mation for an open flow of 34,000,000 cu. ft. of gas per day under a natural pressure of 685 lb. per sq. inch. Oil was discovered in the Powder Wash field on Nov. 26, 1936, in the company's No. I Carl Allen on the NE.SW.SE. of sec. 32-12N-97W. The oil production was

Jan 1, 1941

By W. A. Ver Wiebe

Spurred on by the very high demands for new crude supplies resulting from World War 11, the oil men of Kansas strained every effort in 1943 to find as many new pools as possible. In all, 1761 test wells were drilled, ,of which 895 were successful in finding new oil supplies and 32 in finding new gas supplies. The total number of wildcat wells drilled in Kansas was 577, including the so-called "extension wildcats," which are located less than 2 miles from production. As a result of the very determined effort to find new oil reserves, 49 of the wildcat test wells found new oil pools in western Kansas and 7 found new oil pools in eastern Kansas. There were 289 rank wildcat tests, and among these 28 were successful ventures. They are responsible for 26 of the new oil pools recorded for the year and 2 of the new gas pools recorded. The ratio of dry holes to producing wells among such rank wildcats is thus approximately 10 to I (289 dry and 28 good). This compares with a ratio of II: I in 1942 and 6:1 in 1941; the same in 1940 and 5:Iin 1939. With nearly all wells flowing to their maximum economic capacity, the total production for Kansas during 1943 reached a new high; that is, 107,700,000 bbl., compared with 97,000,000 during the previous year. Similarly, the amount of gas sold during 1943 made a new high point on the production curve. The total amount was 122 billion cubic feet, compared with about 98 1/2 billion cubic feet for the year previous. As usual, the large Hugoton field of south- western Kansas accounted for approximately half of the total gas production. Highlights of the Year Despite the fact that 56 new pools were found in Kansas during 1943, it must be admitted that the future reserves of the state have not been increased greatly. Most of the new pools seem to be of minor value, although it is admittedly impossible to gauge the future production of any pool in Kansas with any exactitude. Judging by the later performance of some of the pools found in 1942 and in 1941, less than five of the new pools are likely to make any great contribution to the state's future oil reserves. Taking up the counties of Kansas in alphabetical order, the following statements summarize the highlights of the year. In Graham County, the Morel pool was extended to the southeast and this pool now promises to become one of the important pools of western Kansas. Several of the older wells have already contributed more than I000,000 bbl. of oil, and such a figure is considered very satisfactory in Kansas. In McPherson County, important new reserves were found by persistent drilling in township 17 S., R. I. W., the most northeastern township of the county. Many new wells in older pools and discovery wells in new pools make this region look promising. The Lindsborg pool, which had a sensational revival during 1942, was also extended in a number of directions and has now become a rather large producing area with a fairly high future potential capacity.

Jan 1, 1944

By S. R. Dunbas, D. C. Jillson, E. A. Anderson

THE present work was undertaken to furnish information, lacking in the literature, on the deformation mechanisms active in pure titanium at room temperature. Since it was started, Rosi, Dube, and Alexander' have indicated that slip can occur in coarse-grained (2 to 6 mm diameter) titanium on the {1010} and {1011} planes and twinning can take place on the {1072}, (1122) and (1151) planes. Liu and Steinberg,' working with titanium flakes produced by fused salt electrolysis, found evidence of twinning on the {1032$, {1121), {1122}, (1123}, and (1154) planes. The crystals used in the present work were substantially longer (up to nearly 2 in. in length) and possibly purer. Production of Large Crystals It was the purpose of this part of the work to provide single crystal or large grain specimens for use in the deformation studies rather than to study the mechanism of crystal growth. Accordingly, all further exploratory studies on methods were abandoned when it was found that cold-rolled bars sealed in vacuo in individual Vycor tubes and given three or more cycles of 4 hr at 1200°C and three to five days at 850°C, gave large grains. Eighteen specimens about 0.2 in. square x 2 in. long yielded 33 useful grains, ranging from Va in. to nearly 2 in. in length, with an agreeably wide range of orientations, Fig. l. The 0.25 in. thick strip from which the starting specimens were cut had been reduced 67 pct on 18 in. diameter rolls from a scalped, hot-forged (959" to 1000°C), arc-melted, iodide titanium ingot. Thc bar was at room temperature, but the rolls were at 200°C. Reductions of about 0.03 in. per pass were used. The bar was cut into four segments, each of which was rolled in a somewhat different manner. No effect on the growth of large grains was noted. The composition of the titanium, determined on turnings from the ingot scalping operations, is given in Table I. The Rockwell A hardness of the ingot was 26. The standard starting specimens, about 1/4x1/4x2 in., were milled on all four sides, hand polished on 280 and 400 mesh emery papers, etched for 3 min in a 50 HF-50 glycerine solution, rinsed, and dried in alcohol and ether just before sealing them in Vycor tubes. The average specimen weight was 7.5 g, and the tube volume was 6.5 cc. A vacuum of less than 1 micron pressure was applied. The specimen tubes were placed in an evacuated Inconel muffle to minimize the danger of collapse of the glass tubes at temperature. In practice the specimens were first heated to 1200 °C for 4 hr and then transferred fairly quickly to an 850°C furnace where they were held for three to five days. This cycle was repeated at least three times before the specimens were cooled, removed from the tubes, lightly polished and etched on one surface for examinstion. Those in which large grains had not developed were resealed in Vycor and returned to the cycling. Satisfactory specimens (about one out of every four cycled) were polished with emery paper on all four side;, then metallographically polished using ctchinz between wheels to remove distorted metal and, finally, given a very light etch to reveal the grain boundaries. This was necessary because the surface was roughened by the sublimation of titanium under high temperature vacuum conditions. Specimens were identified by TiXl numbers using supplementary letters to designate specific grains.

Jan 1, 1954

By I. R. Kramer

The delay time for single crystals of iron, zinc, and pre-strained aluminum was measured under conditions of high-speed deformation. The delay time of aluminum was found to be affected by the orientation of the crystal. Under the dynamic conditions employed, tile calculated "activated volume" term appears to be very small for the three metals studied. IN a previous paper,1 it was shown that under dynamic testing conditions at 78° K, there was a delayed yield in single crystals of aluminum and copper which had been cold-worked prior to testing. The experimental results also indicated that the delay-time effect was not due to the interaction of dislocations with impurity atoms or vacancies, but rather to a dislocation-dislocation interaction since aluminum which has not been prestrained shows no delay-time phenomenon. In this paper, some data are reported on the effects of orientation on the delay time of aluminum single crystals; the delay time of zinc single crystals saturated with nitrogen and the delay time of iron single crystals also were measured. EXPERIMENTAL PROCEDURE Aluminum (99.997 pct) and zinc (99.999 pct) crystals, 1/2 in. in diam and 8 in. long were grown by the Bridgman technique. The iron single crystal was supplied by Dr. R. Maddin. The zinc crystals containing nitrogen were prepared by melting high-purity zinc in a graphite crucible and the nitrogen was introduced by additions of ammonium chloride. The liquid zinc was then drawn up into glass tubes of 1/2 in. diam and allowed to solidify. The rods were cooled to room temperature before the transfer to the mold for conversion into single crystals. The orientation of all specimens was determined by the Laue' back-reflection technique, Fig. 2 and Table I. To prepare for the delay-time measurements, the crystals were cut with a fine jewelers saw and the ends carefully machined. The specimens then were electrolytic ally polished to remove the cold-worked metal, mounted in a special fixture and hand-lapped. As a final step, the crystals were annealed in evacuated tubes. Specimens of aluminum crystals, Nos. 24 and 26, were compressed 0.5 and 2 pct, respectively, in the direction of the later impact. The zinc specimens were aged at 50°C for 15 min, In the case of iron, only two specimens could be obtained. To obtain sufficient data, it was necessary to resort to a reaging treatment. After each delay-time test, the specimens were aged at 65° C for 100 min. This treatment, according to Clark,2 is sufficient to restore the original delay time. It is believed that although the specimens were plastically deformed approximately 10-4 pct, after each test the delay-time values are reliable. The delay-time measurements were made in an apparatus similar to that described previously.' Single crystals approximately 1 in. long and having a diameter of 1/2 in. were placed in a pendulum which consisted of a bar 1/2 in. in diam and 8 ft long, designed with a crystal holder to accommodate the specimen at low temperatures. The crystal was held at a position 2 ft from the front part of the pendulum. This portion of the apparatus was supported on a fine molybdenum wire. A projectile bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on

Jan 1, 1962

By Robert T. MacMillan

Of all the mineral substances utilized by man, salt or sodium chloride has one of the longest and most varied histories. Because all animal life is descended from marine organisms, sodium and chlorine became necessary to life, and as sodium chloride meets requirements most readily, common salt has been essential to human and animal diets from earliest times. As civilization progressed, man learned to evaporate sea water and brines of saline lakes and springs to obtain salt, and gradually ceased to depend on the flesh of animals and the occasional salt outcrops or "salt licks" they frequented. He also learned that salt had a multitude of uses, particularly as a preservative of meat and other foods. The importance of salt in the minds of early men may be readily seen from many allusions in the Bible and other ancient writings. Expressions such as "not worth his salt," and "the salt of the earth" are deeply embedded in the English language. Salt has symbolized friendship, fidelity, purity, and hospitality. It has been used as currency; had religious significance; caused wars; and has been a favorite commodity for taxation. The English word "salary" stems from the Latin word for salt, in which Roman soldiers received part of their pay. Although salt today retains its dietary importance, it has thousands of other uses. Of each 100 pounds produced in the United States less than three pounds is for table use. The other 97 pounds goes for agricultural, industrial, and chemical uses. Fortunately, reserves of salt are enormous and reasonably well distributed on the face of the earth. The sea is an inexhaustible source of salt which may be had at prices which vary with climate and other factors. In addition, large underground salt deposits and many salt lakes, springs and playas are scattered throughout the world. Most countries have access to a salt supply, although some are more favored than others. Properties Crystallized sodium chloride or common salt is known as halite. Its molecular weight is 58.454 and it contains, by weight, 39.34 pct sodium and 60.66 pct chlorine. Alternate positions in the cubic lattice are occupied, respectively, by negative chloride and positive sodium ions; the crystal form is isometric. Crystallization from water produces concentric shells, and when broken, a crystal shows conchoidal fracture. Salt has a hardness of 2.5; its specific gravity ranges from 2.1 to 2.6 for rock salt and is 2.165 for the pure crystal. The refractive index is 1.554; it melts at 800.8 ± 0.5°C and boils at 1413°C. Its heat of fusion is 123.59 cal/ gram. Salt is transparent or translucent and highly diathermous. It is colorless when pure and has a vitreous luster. Salt containing traces of iron oxides has varying shades of yellow, orange, brown, pink, or red. The peculiar shade of red sometimes found in that produced by solar evaporation of sea water has been attributed to tiny organisms. Blue mottlings sometimes seen in halite crystals have been attributed to colloidal sodium. Salt is soluble in water to the extent of 35.7 parts per 100 parts of water at 0°C and 39.8 parts per 100 of water at 100°C. The small difference in solubility with increasing temperature is important in the economics of producing salt by evaporating brine. Salt has a negative heat of solution which is 1.281 kg-cal/ mole at 18°C in 200 moles of water.

Jan 1, 1960

By R. M. Asimow, J. J. Svitak

Tile crilical resoll,r,d shear stress, CRSS, for slip of slow1y cooled Ag-All single crystals was measured at 201K. Tlze importance of short-range order and Suzuki sogregalion was inrestigated by deter~rlining llze ciic.cl of quenching on the CRSS. Thr obserz.ed rfrtenching effects were generally small and indicate that short-range ordcr and Slczuki srgregation do no1 account for n significant portion of the solid-solution strengthening in this system. However, all alloys slzozcwi yield drops ulhich rilere heat- lreat nrenl-sensiline THERE have been a number of mechanisms proposed to explain alloy strengthening in the Ag-Au system. The effectiveness of some of the proposed mechanisms, especially those that depend on Suzuki segregation1" or on short-range order,2-6 SRO? should be strongly dependent on heat treatment. Since internal friction investigations in this system indicate that there is stress-induced order,' we must also consider the possibility of local atomic rearrangement or short-range ordering in the stress field of a dislocation. There is not complete agreement whether these mechanisms should be most effective in raising the flow stress, in causing yield drops. or some combination of these two effects. This work was undertaken to determine the effects in the Ag-Au system of mechanisms that depend on segregation or order by using known but drastically different cooling rates following a high-temperature treatment. By comparing the critical resolved shear stress, CRSS, for slip measured after a very slow cool and again after a fast cool (quench) of the same crystal, it is possible to determine the effect of cooling rate on CRSS* and on yield drops. The single-crystal CRSS was determined at several compositions because there has been no data published across the phase field since the publication of room-temperature flow stress by Sachs and Weerts.' EXPERIMENTAL PROCEDURE Starting with materials of 99.999 pct purity, single-crystal specimens of random orientation 1.25 mm square by 4 cm long were prepared with 0, 10, 14, 25, 30. 50, 70. 75. 80, 90. and 100 at. pct Au. Crystals were grown in an inert atmosphere using a modified Bridgman technique with a growth rate of 1.5 cm per hr in a gradient of 3°C per cm. To obtain a maximum practical degree of SRO, the crystals were cooled at a rate of 275'C per hr to about 310°C and then cooled at 6°C per hr to approximately 200°C. Specimens were tested in tension immersed in an alcohol bath at -72°C (201°K) at a strain rate > = 0.003 mm"1 to determine the CRSS (7). The activation volume of several crystals was determined from the flow stress increment (72 - T1) for a tenfold increase in strain rate. The total shear strain varied from 0.05 to 2.3 pct but was generally less than 0.4 pct. After testing, each crystal was then held at 500°C for 10 min, quenched into brine at -35°C and. after storage at -71°C for 1 day, retested in tension using a procedure identical to that of the first test. The quenching apparatus, see Fig. 1, was designed to enable accurate temperature control and rapid quenching while preventing specimen contamination and accidental deformation. Test data from a specimen with a fine thermocouple spot-welded to it indicated a cooling rate of 104C per sec. The relatively low heat-treatment temperature was chosen to minimize quenching defects caused by a large vacancy

Jan 1, 1970

By M. J. Pool, with Appendix by Larry Kaufman, R. W. Krenzer

Thermodynmic properties of the Cu-Mn system have been deterrrzined in the temperature range 973" to 1273°K by measuring the vapor pressure of manganese in equilibrium with alloys of compositions varying from 0.13 to 0.91 rnole fraction manganese using the Knudsen effusion technique. Activities of manganese calculated from the measured vapor pressures show large positive deviations. Calculated heats and entropies of mixing are positive with a maximum occurring at approximately 0. 7 mole fraction manganese. ThE investigation of thermodynamic properties of binary systems involving transition metals is of considerable interest at the present time. The incomplete subvalency electron levels of transition metals lead to unusual behavior in some alloys, and considerable information can be obtained by determining the thermodynamic characteristics of these systems and relating the thermodynamic behavior to observed physical properties. The Cu-Mn system, shown in Fig. 1,' provides an example of an alloy system in which the determination of the equilibrium phase diagram and various physical properties has received considerable attention, but very little work has been done on measurement of the thermodynamic properties. Elemental copper and manganese have comparable electronegatives, atomic sizes, and cohesive energies, but differ in crystal structure. They form a continuous series of solid solutions only at high temperatures and the structure varies in a continuous manner from fcc at the copper-rich end to fct at the manganese-rich end.' The purpose of this investigation was to measure the vapor pressure of manganese over a series of Cu-Mn alloys and from these values determine the thermodynamic properties of the binary system. Vapor pressure measurements were made in the temperature range 973" to 1273"K, remaining within the solid-solution region for each alloy studied. EXPERIMENTAL PROCEDURE The relative thermodynamic properties of solid Cu-Mn alloys were determined from vapor pressure measurements by means of the Knudsen effusion tech- nique. Several discussions of the theory can be found in the literature. In the case of copper and manganese, it is assumed that manganese is the only component subliming, so the vapor pressure of manganese over the various alloys can be determined directly by measuring the weight loss of the effusion cell. This is a valid assumption since the vapor pressure of manganese is about four orders of magnitude higher than the vapor pressure of copper in the temperature region of interest. The vapor pressure of manganese over the alloys at any given temperature is then related to the weight loss of the effusion cell per unit area per unit time. An upper limit of 1.5 x 10"s has been measured for the ratio of polyatomic to monoatomic molecules for manganese vapor in equilibrium with solid manganese at 1180°K, so it was assumed that manganese vapor is monoatomic. The effusion cells, fabricated from high-purity alumina, are 26 mm high, 18 mm OD, and have a wall thickness of 1 mm. Three different sized holes of 2.03, 2.54, and 3.18 mm diam were drilled in the lids from the inside face to minimize chipping, and the lids were then slip-cast onto the cells to provide a gas-tight seal. Alumina was selected for this particular application both because of its resistance to thermal shock and reaction with manganese vapor. In the ideal case, the orifice of the effusion cell should have a knife edge so that effusion through the orifice

Jan 1, 1970

By M. J. Blackburn

The ordering reaction and its effect on dislocation awangements in alloys based on Mg3Cd has been studied by transmission electron microscopy. Ordering occurs by the growth of ordered domains until they impinge, thus producing an antiphase domain boundary (APB) network. In the disordered alloy, slip is confined to the basal plane while in the ordered condition slip occurs on the basal, prism, and pyramidal planes. Superdislocations have been identuied on these planes and their origin and expected spacings are discussed and compared with the observations. The APBs between the dislocation pairs have been resolved and have proved useful in the identification of superdislocations. Observed slip structures are related to the changes in mechanical properties produced by ordering. At high temperatures magnesium and cadmium form a continuous series of disordered hexagonal solid solutions. At lower temperatures three ordering reactions occur; two based on the compositions Mg3Cd and MgCd3 are transformations to DO19-type superlattices while alloys based on the composition MgCd transform to a B19 lattice. The ordering process in alloys near the composition Mg3Cd has been studied by several workers'-4 and it has been shown to be a first-order type transformation. The variation of mechanical properties with the degree of order and temperature have been reported in some detail by Stoloff and Davies.5 It was shown that the disordered alloy was stronger and less ductile than the ordered alloy, the differences being attributed to changes in the number of active slip planes and to the presence of short-range order in the disordered alloy. In this investigation the ordering reaction has been qualitatively followed by transmission electron microscopy. The effect of this ordering transformation on the dislocation arrangements in deformed specimens has been studied in some detail. EXPERIMENTAL Alloys were melted in a stainless-steel crucible under a flux and chill cast; both melting and casting were performed in an argon atmosphere. The ingots were hot-rolled and tensile specimens cut from the resultant strips. Some large-grained specimens were grown by the strain-anneal method. Heat treatment was carried out in inert atmosphere furnaces and in oil baths at the lower temperatures. Thin foils for transmission electron microscopy were produced by electropolishing in a cooled solution (temp = -40°C) containing 50 cu cm of nitric acid and 180 cu cm of methanol at a potential of 10 v. The ordering reaction was followed by transmission electron microscopy, X-ray, and electrical resistivity measurements but this paper will be concerned chiefly with the electron-microscopy results. Much of the work described in this paper was performed on an alloy containing 26.10 at. pct Cd although two of the micrographs are taken from work on a 25.55 at. pct Cd alloy. RESULTS i) The Quenched Solid Solution. Specimens which were quenched from above the critical temperature showed diffuse superlattice reflections. sark-field analysis on these reflections failed to reveal the presence of ordered domains and thus the superlattice reflections were assumed to arise from regions of short-range order. Quenching from temperatures of 400" to 450°C results in the formation of dislocation loops and helical dislocations. Such defects have been observed and analyzed in detail in several hexagonal metals6-' and as the crystallography and interactions of such loops appear similar in this alloy they will not be reported in detail. Fig. 1 shows a high density of loops

Jan 1, 1968

Aamot, Olav Crone, (M'29) Chem. Engr., Elektro¬kemisk, Raadhusgt, 23; Oslo, Norway. Abadilla. Quirico A., (M'33) Min. Engr., Dir., Bureau of Mines, Manila, P. I. Abbott, Agatin T., ( J'40) Asst. Geol., Trench Mine, Patagonia, Ariz. Abbott, Clarence E., (M'04) Civil Engr., V.P., Tennessee Coal Iron & R. R. Co.. 159'3 Brown Marx Bldg.. Birmingham, Ala. Abel, Raymond L., (M'28) Chem. Engr., Chief of Inspection Div., Pittsburgh Chem. Warfare Pro¬curement Dist., American Batik Bldg., Pitts¬burgh. Pa. Abel, Walter D., (M'32) Min. Engr.. Div. of Cor¬porations, State of Calif.. 403 California State Bldg., Los Angeles, Calif. Abele. Louis T., (M'31) 4800 Patterson Ave.. Richmond, Va. Abell, Leo M., (M'311 Research Met., Mount Mor¬gan Ltd., Mount Morgan, Queensland, Australia. Abenius, Hakan V., (M'37) c/o Falu Gruva, Falun, Sweden. Abernathy. G. E., (M '33S) Geol., Kansas State Geol. Survey. Pittsburg, Kan. Abernathy, Jack. H.. (M'40) Chief Engr., Sunray Oil Co.. Philtower B1dg., Tulsa. Okla. Ahorn, Robert H., (M'19) Asst. Met., Research Lab., U. S. Steel Corp., Lincoln Highway, Kearny, N. J. Abraham, A. W., (M'30) Petr. Engr., Richfield Oil Corp., 555 S. Flower St., Los Angeles. Calif. Abramowitz, William L., (J'40) Chem., National Oil Products Co., Harrison, N. J. Abrams, Charles Jackson, (M'36) Gen'l Supt., Climax Molybdenum Co.; Climax, Colo. Abstein, Henry T., (M'27) Yellow Pine, Idaho. Ackerman, D. E., (M'35) McKinsey & Co., 2 Wall St., New York, N. Y. Ackerman. E. Dumont, (A'3S) Petr. Geol.. Dist. Geol., Quiriquire' Dist., Standard Oil Co. of Venezuela, Caripito, Venezuela.

Jan 1, 1941

When the writer first began his search for the early history of coal he was amazed at the paucity of information in literature about it, and while after six years many of the reasons for such a scarcity are understood, there are still many cases, even within the last two centuries, when one who can appreciate the tremendous part coal has played in the development of modern times, finds it hard to realize how little attention was paid to this material in those early clays. Occasionally a traveller or observer is found who foresaw how valuable coal was to be when industries were developed, but these were few and to most of those recording its occurrence it was just another mineral. George Washington was farsighted in his view of the development of this country and the need for means of transportation across the mountain barrier, but it was at least sixteen years after he must first have known of coal before he made any reference to it in his journals. He did, however, knowingly or not, select some valuable coal properties in the lands lie obtained in the West. This was then almost entirely an agricultural country, and what industries there were found a great abundance of wood fuel within easy access, there were no steam plants, and all iron was made with charcoal; in fact, the "captive mines" of the iron industry then were large timber "plantations," and when these were exhausted the furnace usually was abandoned and another one built elsewhere, as transportation of charcoal was quite expensive. Along the seaboard the cities and industries began to import coal from England and Nova Scotia early in the eighteenth century, but until the war of the Revolution began the total quantity of coal used yearly in this continent did not exceed nine thousand tons. In 1800 only two places, Pittsburgh and Richmond, Virginia, were using coal to any extent for domestic purposes and it was much later. than this that the amount of coal used in Philadelphia, New fork, and Boston exceeded that of wood. Practically all of the early travellers and writers mentioning coal are noted in the following pages. Several Englishmen who were evidently familiar with its use and value at home, mention its presence as being of great future promise to the young nation, but to nearly all it was more or less of a curiosity and the smoke caused by its use an abomination, and it

Jan 1, 1942

[A Aall, Christian H., M49 B VP, Dir of Smelt & Refin, Am. Metal Climax Inc., 1270 Ave. of the Americas, N.Y. Aaroe, Stanley L., A54 B VP, The W. S. Tyler Co. of Can. Ltd., St. Catharines, Ontario, Canada Abalos, Toodulo Q., J57 A Prod Foreman, Lepanto Cons. Mng. Co., Mt. Province, Philippines Abbass, G., M55 P. O. Box 680, Hong Kong, China Abbitt, James M., A54 770 Sole Blvd., Bartow, Fla. Abbott, Raymond C., J59 3442 Greenwich Ave., Columbus 24, Ohio Abdullah, N. Y., J53 Dept. of Mines, Res. Div., P. O. Box 1016, Tiger Lane, Ipoh Perak, Malaya Abel, John F., Jr., J53- 100 Maple, Littleton, Colo. Abell, Leo M., M31 B Conc Supt, Phelps Dodge Corp., Morenci, Ariz. Abendroth, Harry E., A57 A Geol, Union Carbide India, 183 Brabourne Rd.. Calcutta. India]

Jan 1, 1961

By W. S. Ayres

A BRIEF history of the growth of the anthracite-coal preparation will give a better view-point from which to judge the present problem of separating slate from coal. At the beginning of the commercial value of anthracite, 70 years ago, only the pure portions, or " splits," of the veins were mined and shipped to market, and without any preparation or screening other than the selection, while loading, of the glassy lumps, and the rejection of the fine material and the slate that had strayed accidentally into the coal. The next step was the crushing or breaking of the coal (hence the name Lt breaker" as applied to the preparation-building), and the sizing of it by means of bars or revolving screens. This stage of its development marked the advent of the "breaker-boy " as a slate-¬picker, with his ever-increasing capriciousness. As the richer veins or ? splits " became exhausted and the market demanded a still greater output, the less-pure " splits " and the thinner veins were utilized to produce the coal. Carrying as they do a far greater percentage of impurities; particularly when removing the pillars, it became necessary to build new and better equipped preparation-plants. Finally, we are now at the highest stage of complication yet known to the art of coal-preparation. We are dealing with varying specific gravities, frictional difference, hardness, structure, and form in the pieces of coal and slate coming from many different veins, and

Dec 1, 1909

[A Aall, Christian H., M49 D Mgr, American Metal Climax, Inc., 61 Broadway, New York 6, N.Y. Aaroe, S. L., A54 B Sales Mgr, The W. S. Tyler Co. of Can. Ltd., St. Catharines, Ont., Canada Abalos, Teodulo Q., J57 A Foreman, Lepanto Cons. Ming. Co., Mt. Province, Philippines Abbass, G., M55 P. O. Box 680, Hong Kong, China . Abbitt, James M., A54 770 Sole Blvd., Bartow, Fla. Abdullah, M. Y., J53 Dept. of Mines Res. Div., P. O. Box 1016, Tiger Lane, Ipoh Perak, Malaya Able, John F., Jr., J53 A Ming Engr, USA SIPRE 1215 Washington Ave., Wilmette, Ill. Abell, Leo M., M31 B Conct Supt, Phelps Dodge Corp., Morenci, Ariz. Abenius, Hakan Wilhelm, M52 A Mng Dir, Stora Kopparbergs Bergslags AB, Falun, Sweden Abenoroth, Harry F., A57 Natl. Carbon India Ltd., 18A Brabourne Rd., Box 217, Calcutta, India Abercrombie, Harry W., J56 1645 Camphor Dr., Lakeland, Fla.]

Jan 1, 1961

By John L. Lamont, Walter Crafts

SECONDARY hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to the secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at 1100°F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader.3 Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to 1100°F, but the mechanism of the process has received little consideration .

Jan 1, 1948

By Ivor Jenkins

PROCESSES employing controlled atmospheres in the heat-treatment of metals and alloys are now well established on an industrial scale, and the general principles involved and the advantages to be gained in the use of the technique have received considerable publicity over a period of years. During this time the greatest emphasis has been on the establishment of the process in industry, the main effort being devoted to development work on various types of atmospheres, their useful fields of application and the design of suitable heat-treatment furnaces in which they are to be used. The various types of controlled atmospheres are fairly well standardized, but there still remains a considerable field for the investigation of related problems, in connection with both the gas-generating equipment and the surface chemistry of the heat-treatment of metals, especially in complex controlled atmospheres. This paper describes certain investigations of this nature that were carried out in England up to 1939. The development of processes employing controlled atmospheres has been associated to a very large extent with the heat-treatment of steels, both because of the major importance of steel in industry and the many diverse and difficult problems of surface chemistry involved when steels of such a wide range of composition are heated in the presence of active gases Controlled atmospheres such as dissociated and burnt ammonia or charcoal gas are used in the heat-treatment of low-carbon and high-carbon steels, but from certain points of view a suitable atmosphere generated by the partial combustion of city gas is to be preferred. Both the ammonia derivatives are comparatively expensive, and even if the burnt ammonia is regenerated, thereby reducing operating costs, the capital expenditure of the gas plant may make it prohibitive for the smaller type of furnace installation. Charcoal-gas generators are not without their operating difficulties: especially those associated with the quality of the charcoal, clinker formation and the removal of carbon dust from the generated gas. City gas has the advantage of being comparatively cheap and "on tap" in most if not all industrial centers. The use of raw city gas as a protective atmosphere in the heat-treatment of steels has been described,1 but it presents certain difficulties because of its complex composition and its explosive nature when mixed with air. These factors, together with the tendency toward sooting at elevated temperatures, arising mainly from the hydrocarbon gases present, all militate against its use as a protective atmosphere in industrial furnaces. The following analysis, based on the analyses of city gas in different localities in Great Britain, indicates the wide limits existing

Jan 1, 1947

By Wittenau, E.

OPERATION of a pilot mill of 100 tons' daily capacity during 1930 and 1931 proved that the copper minerals of the Colorado and Clay sections of the Morenci ore body could be successfully concentrated by the flotation process. Economic conditions caused postponement of further testing work until late in 1938 when the former No. 6 Concentrator at Morenci was converted into an experimental mill of 1500 tons' daily capacity which was known as the Test Concentrator. The Test Concentrator began continuous operation on April 3. 1939, using such crushing and grinding equipment of the No. 6 Concentrator as was appropriate. Modern classifiers and certain flotation machines were installed and later other types of flotation machines, a large grate-type grinding mill. mechanical screens, a short-head cone crusher, and a disk filter were added to the test equipment. Operation was uninterrupted until Dec. 31, 1941.

Jan 1, 1942

By B. S. Butler

The principal ore deposits of Arizona are in the southern, cen-tral, and western portions of the state, which physiographically are part of the Basin and Range province, southwest of the Colo-rado Plateau (Pl. I). The Basin and Range province is characterized by numerous subparallel mountain ranges separated by plains or valleys. Most of these ranges trend northwest to north, parallel to the margin of the Colorado Plateau; but in southeastern Arizona, southern New Mexico, and northeastern Sonora, they trend northward, transverse too the edge of the Plateau. The mountains rise abruptly from plains or valleys, the margins of which in many places are pediments cut on hard rock. Some of the plains form closed basins (bolsons, playas), but most of them are drained. The Basin and Range province in Arizona is divisible into the Mountain Region and the Desert Region4 (Pls. I and II). The Mountain Region forms a belt 60 to 100 miles wide that contains most of the large ore deposits. Its longest range measures about 55 miles, the widest 20 miles, and the highest peak more than 10,000 feet above sea level or 7,000 feet above adjacent valleys or plains. Broad plain-forming valleys are exceptional, but several with maximum widths of 20 to more than 30 miles appear in the southeastern portion. In the Desert Region the mountains are relatively low, narrow, serrated, and steep, with sharply angular profiles. There are a few exceptionally large ranges of which the longest measures nearly 100 miles and the widest 18 miles. The highest peak is some 7,000 feet above sea level, and the maximum local relief amounts to about 5,400 feet. Broad and comparatively low desert plains form 50 to 75 per cent of the area.

Jan 1, 1939