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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 L. K. Jetter, C. J. McHargue

The use of axis charts for representing the texture of cold-rolled thorium sheet was compared with conventional pole figures. Four texture components were deduced from the axis charts and shown to be consistent with the pole figures. It was shown that consideration of the pole figures alone could lead to an apparent component which is the average of two actually present. It was also shown that the spread about the "ideal" textures and the amount of material associated with each could be readily obtained Fom the axis chart method. BECAUSE of the crystallographic nature of the deformation mechanisms in metals, plastic flow results in the alignment of certain crystallographic directions with the primary flow directions. In the study of the "preferred orientation" thus developed, one wishes to discern the distribution of the crystallographic directions with respect to some reference direction, usually a direction related to the fabrication procedure, such as the rolling direction. The pole-figure method, introduced by ever,' involves the plotting of the distribution of the poles of some family of planes on a stereographic projection which places the reference direction(s) at the north pole and/or in the center. By noting the angles between the reference directions and concentrations of poles on several such pole figures, one can deduce the crystallographic directions which are aligned with the reference directions. If the preferred orientation is relatively simple and well-developed, one to three pole figures may be sufficient for obtaining the desired information; if there are several texture components, more pole figures may be needed. A significant improvement in the method of representing the textures in wires and rods resulted from the introduction of the "inverse pole figure" or axis-distribution chart by Harris.2 Such a chart gives directly the distribution of the reference axis relative to the standard stereographic projection. There has been widespread acceptance of this method for the representation of fiber textures, and methods have been proposed for converting observed diffraction intensities into axis densities.2-6 The suggestion by Mitchell and Rowland3 and Jetter, McHargue, and williams5 that sheet textures could be represented as distributions of rolling, normal, and transverse directions have been criticized on the basis that they offer no significant advantage over a combination of two ordinary pole figures and that it has not been proved that sheet textures can be treated as quasi fiber textures.6 If the purpose of a texture determination is to study some property which is related to the orientation of a particular crystallographic plane or direction, then conventional pole figures certainly are sufficient. For example, the distribution of the slip planes in face-centered cubic metals (the (111) pole figure) serves to indicate the variation in mechanical properties of sheet. On the other hand if the study is directed at an understanding of the factors influencing texture formation, it is desirable to know not only the preferred orientation but the kind and degree of spread from it and the relative amounts of material in each component, if there are more than one. Axis charts give this information as well as the orientation distributions. Consider the procedure for deducing a texture component from a pole figure for the (111) planes

Jan 1, 1961

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 J. L. Taylor, Pol Duwez

THE present knowledge of the Ti-Al system is limited to the portion of the diagram extending from pure aluminum to the intermetallic compound TiAl3' A preliminary investigation of the titanium-rich Ti-A1 alloys revealed that the solubility of aluminum in titanium is quite extensive and that the transformation temperature of titanium is raised by alloying with aluminum. From an X-ray diffraction study of alloys containing up to 75 atomic pct Al (TiAl3), the phase boundaries at 750°C were located as follows: the a titanium solid solution extends from 0 to about 36 atomic pct Al, a two-phase region exists from 36 to 46 atomic pct Al, and an intermediate phase of varying concentration extends from 46 to 62 atomic pct Al. The purpose of the present paper is to describe the crystal structure of this new phase. The alloys were prepared by melting in a helium arc furnace on a water-cooled copper plate, using a furnace essentially the same as that described in ref. 2. The titanium metal was of the iodide type furnished by the New Jersey Zinc Co., and a piece of pure aluminum (99.99 pct) was obtained through the courtesy of the Aluminum Co. of America. After melting, the samples, weighing approximately 5 g, were sealed in evacuated fused silica tubes and homogenized for 4 hr at 1000°C. The specimens were then held for 10 days at 750°C and rapidly cooled to room temperature. Filings were then taken from each sample, sealed in evacuated vials, annealed at 750°C for 4 hr, and rapidly cooled to room temperature by quenching the vials in water. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using K copper radiation filtered through a nickel foil. Structure Determination The X-ray diffraction patterns of the alloys containing 46, 50, 55. 60, and 62 atomic pct Al were identical, except for a slight shift in the positions of the reflections. The alloy containing 55 atomic pct Al was chosen far structure determination. The powder pattern contained 37 reflections and the a, doublets were well resolved in the back-reflection range. The relatively small number of reflections and the sharpness of the pattern were considered as an indication of a simple atomic arrangement in a relatively small unit cell of high symmetry, and an attempt was therefore made to solve the structure without single crystal work. A satisfactory fit was found on a large scale Hull-Davey tetragonal chart for an axial ratio of approximately 1.45. All the reflections were readily indexed and the tentative unit cell dimensions were computed to be a - 2.81 kX, c - 4.07 kX, and c/a = 1.448. The indices (hkl) and the values of d and sin2 A are given in Table I. The agreement between observed and computed sin2 is quite satisfactory. Once the unit cell was known, the details of the structure were readily found. First, it is obvious that the number of atoms per unit cell cannot exceed two, since more than two atoms would lead to a density greater than that of pure titanium. The next logical step is to assume that the two atoms occupy the corner and center of the cell. If this assumption is correct, the structure may be described as follows: space group D1, - P 4/mmm; one titanium atom in a: 000; one aluminum atom in d: 1/2 1/2 1/2: and no extinctions. Assuming this structure to be the correct one. intensities were computed by means of the usual equation: sin2 0 cos 0 where F is the structure factor; 8, the Bragg angle. and p, the multiplicity factor. The calculated values of intensities are compared in Table I with the visually estimated intensities. The agreement is quite satisfactory and the structure is therefore confirmed. The crystal structure of TiAl just described is the same as that of AuCu ordered. The AuCu ordered

Jan 1, 1953

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 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 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 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 B. Post, F. W. Glaser

Three borides of zirconium have been reported: ZrB,l ZrB2,2,3 and ZrB12, 4 The phase relationships, ranges of stability, and some physical properties of these compounds are described. THE zirconium borides differ considerably from one another, particularly with respect to their relative stabilities at high temperatures in the presence of carbon.4,5 ZrB2 is extremelv stable at all temperatures (to the melting point) in contact with carbon. Both ZrB and ZrB12 tend to decompose at elevated temperatures when carbon is present in excess of about 0.5 pct. ZrB forms ZrB2 and ZrC, and ZrB12 decomposes to form ZrB2 and a boron-carbide phase. In the ZrB12 preparation, boron present in excess of that needed to form ZrB2 reacts with carbon, if present, to form carbides, in preference to forming the higher boride. Similar instability of borides, other than diborides of the transition metals of the 4th and 5th groups of the periodic table, has been reported.5,6 special precautions had, therefore, to be taken to minimize carbon contamination in the preparation of ZrB and ZrB12. Reactions below 1400°C were carried out by heating powdered mixtures of zirconium hydride and boron in quartz tubes in a hydrogen atmosphere. For temperatures above 1400°C, reactions were carried out in graphite molds. Carbon contamination from the molds was minimized by employing extremely rapid heating rates to reduce carbon diffusion into the body of the specimen, and by subsequent "shaving" of sample surfaces that had been in contact with the graphite dies. A heating rate of about 2000°C per min was obtained by heating the dies (by direct conduction), using a current of 40,000 amp. Although this type of heating cycle apparently allowed little time for "homogenization," close approximations to equilibrium conditions were usually obtained as a result of the very strongly exothermic reactions between zirconium hydride and boron at elevated temperatures. Reproducibility of results in repeated runs under varying conditions was taken as a reasonable indication that equilibrium conditions had been effectively achieved. Quenching was accomplished by rapidly immersing the entire die, containing the reaction products, in water. Specimens could also be cooled at controlled rates by adjustment of the rate of flow of water through the water-cooled copper electrodes in contact with the graphite dies.

Jan 1, 1954

By C. Norman Cochran, James L. Brandt

ALTHOUGH gas in aluminum and its effect on aluminum products have been the subject of a number of papers, not many quantitative determinations of the hydrogen content of solid aluminum and its alloys have been recorded in the literature. For solid aluminum samples, four investigators have reported hydrogen contents which appear reasonable compared with the hydrogen solubility of 0.7 ml per 100 g, STP, in molten aluminum at 660°C established by Ransley and Neufeld' and verified by Opie and Grant' and Ransley and Talbot. Sloman," who used a vacuum fusion procedure, reported the hydrogen content of some high purity aluminum as 0.66 ml per 100 g, STP. Griffith and Mallett, employing the tin fusion method, reported the internal hydrogen content of six different aluminum alloys as ranging from less than 0.1 ml per 100 g, STP, for 1100 alloy to 0.7 ml per 100 g, STP, for 4043 alloy (previously 43S, a 5 pct Si alloy). Eborall and Ransley," using a solid extraction of the gases at 600°C, reported hydrogen contents ranging from 0.1 ml per 100 g, STP, to 1 ml per 100 g, STP. Ransley and Talbot reported that several thousand analyses on 99.2 pct and higher purity aluminum as well as Duralumin type alloys indicated hydrogen contents ranging from 0.1 ml per 100 g, STP, to 0.5 ml per 100 g, STP.

Jan 1, 1957

By AIME AIME

BLANDFORD. C. BURGESS, the new Chairman of the Industrial Minerals Division, took the advice of Horace Greeley in reverse-he turned his hack on San Francisco and the Golden Gate, and after a few side excursions toward Alaska and Arizona, hit the trail eastward, not for the lonesome pine, but for Spruce Pine, N. C. Born Aug. 10, 1893, in San Francisco. Burgess found his first job, shortly after finishing high school at 19, as axeman for a surveying party of engineers working for the Southern Pacific Co. in Oregon. Later he moved on up with them into Alaska. He liked the engineering profession, and decided to equip himself further so he entered the University of California in the fall of 1913. and for the next two years devoted himself to acquiring an education in civil engineering.

Jan 1, 1945

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By John M. Kelly

New Mexico produced 39,751,868 bbl. of oil in 1941 and ranked seventh among the oil-producing states. Its 1941 production established an annual record, exceeding the 1940 record year by 854,498 bbl. The average daily production for the year was 108,909 bbl. The average daily non-marginal well allowable for New Mexico on Jan. I, 1941, was 36 bbl.; at the close of the year it was 43 bbl. The average daily pipe-linc runs were approximately 3 per cent less than the allocations of the New Mexico Oil Conservation Commission, which followed closely the recommendation of the United States Bureau of Mines in setting the daily outlet demand. The production in Lea County was 34,333,448 bbl.; Eddy County, 5,009,354 bbl.; and northwestern New Mexico (San Juan and McKinley Counties), 406,306 barrels. The total number of completions in the state was 402, of which 301 were oil wells, 19 gas wells, and 82 dry holes. Drilling during 1941 was 68 per cent of 1940, and the ratio of dry holes to producers, I to 4, was the greatest since 1935. Of these dry holes 43 were drilled in proven fields and 39 were wildcats. One new oil field and one new gas field were discovered as a result of the 1941 wildcatting program. However, numerous extensions were made to the existing fields, which, although they were called extensions to proration areas, were in reality field discoveries, being on separate geologic structures. Southeastern New Mexico Lea County The Monument field was the largest producing field in Lea County, with 6,973,808 bbl. It was closely followed by the Eunice field, with 6,644,181 bbl.; Vacuum field, with 4,800,608 bbl. and Hobbs, with 3,624,159 bbl. Hobbs field, however, still has the largest total recovery, this being 97,407,929 bbl. at the end of 1941. The new oil-field discovery in Lea County during 1941 was the Salt Lake field, T. 20 S., R. 33 E. The discovery well was Leonard-Welch State No. I, NW. NW. of sec. 18, T. 20 S., R. 33 E. This well was drilled to a total depth of 3103 ft. and was completed for an initial production of 250 bbl. per day pumping. The oil is 26" gravity and the producing horizon is in the San Andres limestone of Permian age. The discovery well was completed on June 22, 1941, and since that date four more producers have been completed, with no failures. The area is about 10 miles north-west of the Lynch pool, to which the oil from this field is being trucked because there is no pipe-line connection. The greatest drilling activity during 1947 was in the Maljamar field of western Lea County, with 62 completions, 59 being oil wells and 3 dry holes. The limits of this pool are now being defined on the north and south but to date have not been defined either to the east or west. The total number of 40-acre oil-producing units in the field at the close of the year was 158. On April I, 1941, a pressure-maintenance project was installed at the southern end

Jan 1, 1942

By John M. Kelly

New Mexico produced 39,751,868 bbl. of oil in 1941 and ranked seventh among the oil-producing states. Its 1941 production established an annual record, exceeding the 1940 record year by 854,498 bbl. The average daily production for the year was 108,909 bbl. The average daily non-marginal well allowable for New Mexico on Jan. I, 1941, was 36 bbl.; at the close of the year it was 43 bbl. The average daily pipe-linc runs were approximately 3 per cent less than the allocations of the New Mexico Oil Conservation Commission, which followed closely the recommendation of the United States Bureau of Mines in setting the daily outlet demand. The production in Lea County was 34,333,448 bbl.; Eddy County, 5,009,354 bbl.; and northwestern New Mexico (San Juan and McKinley Counties), 406,306 barrels. The total number of completions in the state was 402, of which 301 were oil wells, 19 gas wells, and 82 dry holes. Drilling during 1941 was 68 per cent of 1940, and the ratio of dry holes to producers, I to 4, was the greatest since 1935. Of these dry holes 43 were drilled in proven fields and 39 were wildcats. One new oil field and one new gas field were discovered as a result of the 1941 wildcatting program. However, numerous extensions were made to the existing fields, which, although they were called extensions to proration areas, were in reality field discoveries, being on separate geologic structures. Southeastern New Mexico Lea County The Monument field was the largest producing field in Lea County, with 6,973,808 bbl. It was closely followed by the Eunice field, with 6,644,181 bbl.; Vacuum field, with 4,800,608 bbl. and Hobbs, with 3,624,159 bbl. Hobbs field, however, still has the largest total recovery, this being 97,407,929 bbl. at the end of 1941. The new oil-field discovery in Lea County during 1941 was the Salt Lake field, T. 20 S., R. 33 E. The discovery well was Leonard-Welch State No. I, NW. NW. of sec. 18, T. 20 S., R. 33 E. This well was drilled to a total depth of 3103 ft. and was completed for an initial production of 250 bbl. per day pumping. The oil is 26" gravity and the producing horizon is in the San Andres limestone of Permian age. The discovery well was completed on June 22, 1941, and since that date four more producers have been completed, with no failures. The area is about 10 miles north-west of the Lynch pool, to which the oil from this field is being trucked because there is no pipe-line connection. The greatest drilling activity during 1947 was in the Maljamar field of western Lea County, with 62 completions, 59 being oil wells and 3 dry holes. The limits of this pool are now being defined on the north and south but to date have not been defined either to the east or west. The total number of 40-acre oil-producing units in the field at the close of the year was 158. On April I, 1941, a pressure-maintenance project was installed at the southern end

Jan 1, 1942

By R. R. Vandervoort, W. L. Barmore

Tensile creep experiments were conducted on high-purity, poly cvystalline rhenium from 1500" to 2300°C at stresses from 1500 to I0,OOO psi in a vacuum of 10-a torr. The apparent activation energy for creep was 60 kcal per mole, and the steady-state creep rate varied directly with stress to the 3.4 power. Dislocation substructure that developed during creep was studied by transmission electron microscopy. Possible rate-controlling deformation mechanisms are discussed. The creep behavior of most metals at elevated temperature can be represented by the following equation:&apos;&apos;&apos; t = Cf(s)(^)(s/E)nD [1] where i = steady-state creep rate, C = constant, f(s) = a function involving microstructure, s = applied stress, E = the average elastic modulus at test temperature, n = constant, D = diffusion coefficient According to this well-established relationship, metals with higher elastic moduli and lower diffusion coefficients should have greater creep resistance at the same stress and temperature and equivalent mi-crostructures. While no diffusion data are available, the diffusivity of rhenium should be less than that for most other refractory metals because of its high melting point and hcp crystal structure. The Sherby-Simnad relation for calculating atomic mobility in metallic systems3 predicts that the diffusion coefficient for rhenium is less than that experimentally determined for tungsten4 in the temperature region 1500. to 2200°C. At these temperatures the elastic modulus for tungsten5 is only slightly larger than the extrapolated modulus for rhenium.6 Thus, rhenium is a good possibility for a a high-temperature structural material, but few data on the creep of rhenium have been reported. This investigation was undertaken to study the high-tempera-ture deformation behavior of rhenium in detail. EXPERIMENTAL TECHNIQUES The material used in this study was consolidated from high-purity powder. After cold pressing the powder to a plate a in. thick, the billet was sintered in hydrogen at 2250°C for 24 hr. The plate was reduced to 0.100 in. by cold cross rolling with intermediate anneals at 1650°C for 20 min between passes. The plate was further reduced to 0.060 in. by unidirectional cold rolling with similar heat treatments between passes, and then finally stress-relieved in hydrogen at 1650°C for 30 min. Specimens tested at 1900°C and below were pretest-annealed at 1900°C for 2 50 hr. Specimens tested above 1900°C were pretest-annealed at 2400°C for 5 hr. The impurity content in the "as-received" plate was quite low, table I. Essentially no change in impurity levels was detected in specimens after creep testing. All creep tests and annealing treatments were conducted in a vacuum of 10-8 torr in a test furnace heated by a tungsten mesh element. The load was applied to the specimens through a bellows, and stresses were maintained to ±1 pct of the selected value by periodic corrections for changes in specimen cross-sectional area during creep and for changes in the bellows spring force due to load column extension. One-inch-diameter tungsten force rods were used in the hot zone of the furnace. Deformation at temperature was measured by optically tracking gage marks on the specimen. Temperature was measured by a calibrated optical pyrometer and was determined to ±5"C. Grain sizes were determined by the linear intercept method and specimens were examined in the "as-polished" condition, using polarized light. Specimens annealed at 1900°C had a grain size of 52 ± 5µ , and those annealed at 2400°C had a grain size of 148 * 11 µ. Pieces were cut from the gage section of creep-tested specimens and planed to a thickness of about 0.010 in. by spark discharge machining. Thin foils for viewing by transmission electron microscopy were obtained by electropolishing in a solution of 6:3:1 ethyl alcohol, perchloric acid, and butoxy ethanol, respectively, using the window technique. Bath temperature was —4OoC, and the cell potential was 35 v. The foils were examined in Siemens Elmiskop I, operating at 100 kv. RESULTS AND DISCUSSION In order to analyze the results from creep experiments, Eq. [I] is rewritten in the following form: <=Kf(s)ne-/RT [2] where K = constant, ?// = apparent activation energy for creep,

Jan 1, 1970

By A. J. Jacobs, J. W. Spretnak, R. Speiser

The activities of nickel in liquid iron-nickel solutions containing from 10 to 90 at. pct Ni were measured over the temperature range .1510° to 1600°C. A special function was devised whereby activities can be computed by a graphical integration using the results of chemical analyses on the vapor phase alone. The liquid solutions studied exhibit negative deviation from Raoult&apos;s law, but they approach ideality as the temperature is raised from 1510° to 1600°C. The maximum heat of solution is less than -8.0 kcal per mole. The entropy of solution is less than —2.5 kcal per mole deg at 1510°C, and changes negligibly as the temperature is raised. The liquid iron-nickel solutions do not follow regular solution behavior. THE activities of the components of a liquid alloy system can be determined in favorable cases from the partial pressure of the vapor in equilibrium with the liquid alloy.&apos; Assuming that the vapor over the alloy behaves as an ideal gas, the activity of component i is given by the expression, Where the superscripts 1, v, and o signify the liquid, the vapor, and the pure component, respectively; the f&apos;s are the fugacities, and the P&apos;s, the pressures. The quantities Pi and Pi can be determined by the

Jan 1, 1960

By Paul L. Burkhart

THOUGH at an earlier period brief studies had been made by the Lehigh Navigation Coal Company Inc., it was not until 1924 that J. B. Warriner, then general manager, called for a comprehensive study of timber treatment, treating solutions, and related operations. Because of the impossibility of procuring accurate costs and other pertinent treating data, the American Wood Preserving Co. agreed to treat a car of mine timber at the Port Reading plant of the Reading Railroad. Fig. I shows the treating data collected at the treating plant on this timber, which was installed in two of the Lehigh mines in 1925. [ ] In the latter part of 1925, a survey of the tunnels and gangways of the company&apos;s Panther Valley mines was made to determine the proportion of gangways or tunnels timbered, cause of timber failures, approximate life of the average wood set and the approximate percentage of treated timber that it would be profitable for the company to use. Results of this survey appear in Table I. Because of the high percentage of timber that gave evidence of failure by rot, as noted in Table I, and a further study of the life of the sections where timbering was necessary, it was deemed advisable to fill 25 per cent of the yearly gangway timber requirement with treated timber. QUANTITIES AND TREATMENTS OF TREATED TIMBER PURCHASED In the early days of the program, none of the large treating companies would accept orders for small quantities of treated timber and the company was compelled to state the quantity of timber it would require at each operation in each month of the year. Table 2 is an example of the tabulation given to the various treating companies to assist them in making a yearly bid on the minimum quantity of timber required by the company during the year 1931. A bill of timber was calculated for each car, the weight of which would be between the minimum and maximum weight permitted for railroad-car loading. The treating company was paid for timber upon delivery at the operation specified. As extra cars of timber were required, they were ordered from the treating company, and payment was required on their receipt, on the basis of the piece or tonnage

Jan 1, 1942

By John W. Cabot

The following series of analyses, which may, be of interest to Bessemer-steel makers, is submitted as a contribution to the muchvexed discussion of manganese in Bessemer steel. They were made by the writer in the spring of 1881, at the works of the Pittsburgh Bessemer Steel Company Limited, during a&apos; period of about eight days, part of. which time the rail-steel showed great variation in rolling qualities. During the first part of tile time in question, it rolled well; later on it began to roll wome until, finally, it cracked very badly, reaching its worst stage. After this it rapidly improved until it again rolled smoothly. During this time of transition from good rolling to bad, and hack to good again, the course of the manganese was followed quite closely. It is the striking correspondence between these varying manganese contents and the differences in rolling which is here presented as worthy of notice. The other ordinary elements were determined occasionally, but showed no. unusual variation: The steel, in question, was ordinary rail-steel of about the following compusition : C=35. P - .08. Mn - .98. Si = .08. 8 = .06. The samples for manganese determinations were taken at first from an average of two days&apos; work, and later on, when the steel

Jan 1, 1882

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By H. H. Hausner, S. Storchheim, J. L. Zambrow

The solid state bonding of aluminum to nickel was studied as a function of temperature, pressure, and time at pressure. The initial results indicated that as the reaction conditions were varied, marked changes in tensile strength occurred. Plots of the log penetration coefficient vs the reciprocal of absolute temperature for various isobars were straight lines displaced from each other. THE techniques of bonding different metals to A each other include brazing, welding, welding by application of a molten phase, and solid state welding without any molten phase present. This last technique, the pressing of metals either at room temperature or at some temperature below the melting point of the metals to be joined, seems to offer interesting possibilities for bonding purposes. However, this technique has not been completely investigated, and very little is known about the diffusion phenomena which occur during solid state welding. Some previous work on the effect of pressure on diffusion1 was inconclusive. This paper is concerned with an investigation regarding the effect that the processing variables, such as pressure, temperature, and time at pressure, have in solid state bonding. The tests were made with aluminum and nickel and special emphasis was given to the strength of the bond between these two metals and to the intermetallic penetration rate during the bonding process. It seems that the effect of pressure on the intermetallic penetration is of particular importance for practical purposes and this effect was therefore studied in detail. Procedure Apparatus: The means of solid state bonding used for this study was that of the hot-pressing technique. This method requires the equipment pictured in Fig. 1 and involved the following procedure. The two metals to be bonded were placed in an aquadag lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diameter made of the same material. A thermocouple

Jan 1, 1955