Search Documents

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of' nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150' C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-'' of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami's slution' and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, 'Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

Discussion of the paper of M. B. YUNG, presented at the Pittsburgh meeting; October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2451 to 2458. T. T. READ, New York, N. Y.-I might .point out that this paper of Mr. Yung's is on a field that is comparatively little known. It is not as well known as the Kochiu tin field, of Yunnan, which is probably the third . in tin output of the world. This field under discussion is considerably further west and the tin which is produced here is, according to Mr. Yung, of somewhat higher grade than the Yunnan tin, and is used by the refiners at Hong Kong to improve the grade of the Yunnan tin. Most of you know that the tin from the Yunnan is shipped to Hong Kong, where it is refined and shipped to Europe. Mr. Yung points out that the Fu Chuan deposits are entirely alluvial and not found in any veins. They .differ in that from the Kochiu deposits, which Leclere says are "nullement alluvionels; leur origéne filonienne est de plus evidentes." Granite is the country rock here; doubtless the tin occurred in veins in the granite, and the deposits have resulted from the disintegration of the granite. This is a country of strong erosive agencies. The country is semi-tropical, and the rainfall is heavy, so that one would naturally expect deep surface erosion of this kind.

Jan 4, 1915

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country's production. The largest previous year's consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943

By F. C. Frischknecht

Most early development and application of electromagnetic prospecting methods took place in Scandinavia, where geological conditions favor their use. In other parts of the world these methods have aroused cycles of interest, but in Scandinavia they have been used continuously and successfully since the 1920's. Electromagnetic methods may be classified into two general groups. One group includes methods in which the source of the electromagnetic field remains stationary while the receivers are moved about to explore the area. The other includes procedures in which the energizing and receiving systems are moved together. Other classifications could be based on the size of the energizing source, the particular components of the electromagnetic field which are measured, or the mode of transporting the equipment. The difference between fixed-source and moving-source methods, however, is of such great fundamental importance that it will be emphasized in this discussion. FIXED-SOURCE METHODS Essentially, a fixed-source method consists of the measurement of electromagnetic fields about the source. The mutual coupling between the source and the earth is constant, but the mutual coupling between the receiver and the earth (unless the earth is homogeneous) and also between the source and the receiver changes at each station. The results are usually normalized by relating the field data to the calculated free space or primary field. Turam and Radio Reference Signal Methods: The turam or two-frame* (see Fig. 1A) is probably * Turam means two-coil. the most common fixed-source method. The energizing source is an insulated cable grounded at both ends or formed into a large rectangular loop. Measurements are taken along a traverse at 5 to 50-meter intervals using two small receiving coils, the lagging coil being placed at the position previously occupied by the leading coil. The complex ratio (i.e., inphase and out-of-phase ratios) of the voltages induced in the two coils is measured. Operating frequency range is about 100 to 800 cps. In a typical turam survey a straight, grounded cable several kilometers long is laid out parallel to the probable strike of the ore deposits or conducting strata being sought. An area extending 1 or 2 km on each side of the cable, and within 1 or 2 km of the ends of the cable, is surveyed. Measurements are made at stations 5 to 25 m apart along traverses perpendicular to the cable. Measurements may be made along lines parallel to the cable to serve as base lines for the traverses or for other special purposes. Commonly the receiving coils are oriented with their planes horizontal so that only the vertical component of the field is measured. If additional information is required, one of the hori- zontal components may also be measured by orienting the coils with their planes vertical. In a modified turam technique developed recently for both ground and airborne measurements (Fig. 1B) the amplitude of the complex voltage induced in a single receiving coil is measured and its phase compared with that of a reference signal transmitted from the energizing system by a radio frequency carrier. Thus the un-normalized field is obtained directly, whereas with the turam method it is obtained by calculation from the ratios. The turam method and its modifications have a greater working depth than the other electromagnetic procedures used in ore prospecting. Under favorable conditions conductors have been located at depths of 200 to 300 m. A modified turam method with one of the electrodes grounded in the upper end of a plunging orebody was used to follow the extension of this body to a depth of 200 m beneath a layer of conducting schists. Straight grounded cables are usually preferred to insulated loops because they are easier to lay out and because they often make the method more sensitive. The greater sensitivity of a grounded cable is a result of ground return currents which may flow in the orebodies in addition to the eddy currents caused by induction from the current in the cable. Anomalies in the vertical field due to eddy currents are characterized by a correspondence between high values for the inphase component and positive out-of-phase components and/or low values for the inphase component and negative out-of-phase components. Also the inphase component may approach zero, but it does not become negative. In very long continuous conductors that are parallel to a grounded cable the effect of ground return currents may far exceed the effect of eddy currents. These ground return currents cause a lack of correspondence between the inphase and out-of-phase components and may cause negative inphase or anti-phase components. It becomes difficult to carry out the measurements and often difficult to interpret the results. Such results immediately suggest the presence of graphitic strata, however, since ore deposits are rarely extensive enough to accumulate sufficient ground return current to cause these results. A cable laid out perpendicular to the strike or an insulated loop is sometimes used in areas where graphitic schists and slates are present. Anomalies are then completely or almost entirely due to eddy currents and are easier to interpret. The measured voltage ratios are normalized by either subtracting or dividing by normal field ratios calculated from free space considerations. The normalized ratios are then plotted as individual profiles. When significant anomalies occur in the ratio measurements, the actual normalized fields are calculated by beginning with a measured or an assumed value for the field at a point near the cable and successively multiplying this value by the normalized ratios. There is a similarity between this process and a numerical integration of the ratio curve. Conversely, in many respects the ratio curve is similar to the first derivative of the field curve.

Jan 1, 1960

By F. George, W. Tice, M. Salkind

It was found that Al-A13Ni could be readily cold rolled perpendicular to but not parallel to the whiskers. Reductions of more than 98 pct were achieved without cracking by rolling perpendicular to the whiskers, whereas extensive edge cracking was noted after only 15 pct reduction when rolling parallel to the whiskers. The longitudinal and transverse tensile strengths were nearly doubled, and the longitudinal yield strength more than tripled by cold rolling 50 pct in a direction perpendicular to the whiskers. The whiskers exhibited some waviness (elastic bending) as a result of cold rolling, but at very high reductions (greater than 75 pct) whisker fracture and misalignment became significant. A fine dislocation substructure in the matrix consisting of cells attached to the whiskers was pro -duced by cold rolling. Most of- the substructure was readily removed by a 1-hr anneal at 500°C. Cold rolling was found to substantially reduce the thermal stability of the microstructure at 610°C but did not affect the stability at 500°C. FIBER and whisker reinforced composite materials promise significant improvements in properties over conventional materials. Before they find wide use, however, it will be necessary to understand the response of these highly anisotropic materials to common metalworking processes. Most of the nonmetal-lic fiber reinforced materials have very low elongations (a few pct or less) in the direction of fiber alignment. Thus, metalworking techniques such as rolling and forging would not be as broadly applicable to these materials. This investigation was initiated to determine how a composite system consisting of Al3Ni whisker reinforced aluminum responded to rolling, what changes in the microstructure occurred, and the effect of deformation on the mechanical properties. The composite material studied was produced by unidirectional solidification of the A1-Al3Ni eutectic alloy'-7 and consisted of 10 pct by volume of aligned whiskers of Alai in a matrix of aluminum. It should be pointed out that this system is not representative of all composite materials, and the results will therefore not be universally applicable. The A1-Al3Ni system is characterized by: 1) A strong fiber-matrix interfacial bond 2) A ductile matrix 3) A sufficiently low fiber content to allow significant plastic flow between fibers 4) Strong, completely elastic whiskers (tensile strength 400,000 psi, elastic modulus = 20 X 106 psi.1 These factors allow the material to be readily rolled perpendicular to the fibers. If the fiber-matrix bond were not strong, such a weak interface could fail during rolling. A measure of the ability of a composite to be rolled in the transverse direction can be obtained from noting the transverse tensile behavior. In the case of Al-Al3Ni,2 there is considerable ductility (15 to 30 pct). In the case of boron filament reinforced aluminum, for example, the transverse elongation is less than 1 pct,8 and the material could probably not be cold rolled as readily in that direction. EXPERIMENTAL PROCEDURE 3-in. diam ingots of A1-A13Ni eutectic were unidi-rectionally solidified in graphite crucibles. The starting materials consisted of 99.99+ pct pure nickel and aluminum, and the pure eutectic ingots were made with 6.2 wt pct Ni. The unidirectional solidification process (described in detail elsewhere1-3) consists of preparing a master heat of eutectic composition, remelting, and withdrawing the ingot vertically downward through the heat source at a controlled rate so that plane front solidification proceeds upward at a constant velocity. The resulting microstructure consists of 10 pct by volume of whiskers of very high aspect (length to diameter) ratio. The fiber lengths have not been measured because of the difficulty of detecting fiber ends9 but exceeds 104. There is some possibility that the fibers may be continuous within one grain. Flat sheet specimens 2¾ in. sq and approximately 0.2 in. thick containing whiskers parallel to the plane of the sheet and to one edge were used for this study. A1-A13Ni exhibits either a rod-like (high solidification rates) or a blade-like (low solidification rates) whisker morphology,1,3 and both types were studied. Rolling was accomplished using a two-high rolling mill at a speed of approximately 10 fpm. The rolling direction was either parallel to or perpendicular to the direction of growth (direction of whisker alignment). Reductions of from 0.002 to 0.03 in. per pass were used with the most common value being 0.005 in. per pass. Cold rolling of Al-Al3Ni to more than 98 pct reduction in thickness was accomplished with no intermediate anneals. In addition. a series of speci-mens was cold rolled 97 pct with a 1-hr, 500°C anneal in air after each 50 pet reduction. Tensile testing was accomplished using a Tinius-lsen four screw testing machine. Flat sheet specimens + in. wide and between 2 and 2; in. long with the thickness dependent upon rolling reduction, were used. The gage section was in. wide and 1 in. long. Strain was measured using a clip-on LVDT extensome-

Jan 1, 1970

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

Albert Ladd Colby, New York, N. Y. (communication to the Secretary†):—I observed (Trans., xxxvii., 585) that to obtain tenders from several American mills, the foreign engineer should modify his maximum phosphorus to 0.10 per cent., not as Mr. E. Windsor Richards quotes me, that no American rail-maker can produce rails under 0.10 per cent. of phosphorus. Mr. Richards claims that no English engineer would agree to accept 0.10 per cent. of phosphorus on any terms whatever. Mr. Webster writes that only after an engineer has .been convinced that rails can be made in America equal in every respect to those he is getting abroad, should he be asked to modify ally conditions in his specifications. I know it to be a fact that during recent years in many cases, as, for instance, When delivery could be secured more promptly in the United States than in Europe, the consulting engineers of several British and colonial railroads have frequently agreed to modify their phosphorus requirement to a maximum of 0.10 per cent., and the rails delivered' under these modified specifications have, under like conditions, given just as satisfactory service and proved to be no more brittle than similar sections of 0.07 per cent. phosphorus rails, rolled in England under the same specification except without modification as to phosphorus. Furthermore, it would appear from the analyses of British rails, quoted by E. A. Dancaster,2 in his discussion of Mr.

Jan 1, 1908

By AIME AIME

CHARLIE WARNER, Chairman of the Petroleum Division, is no stranger to the problems of the oil industry or to those of the Petroleum Division, after more than 25 years of experience in locating and producing oil and more than 22 years of membership in the Institute. He was born at Jefferson, N. Y.. April 27, 1894, and educated in the public schools of New York State and at Cornell University where he studied geology and allied sciences from 1913 to 1917 and received a B.A. degree. Immediately upon completion of this training, he was employed by the Empire Gas & Fuel Co. as a field geologist in Oklahoma and Kansas. Two years later he became district geologist for the Emerald Oil Co. in Oklahoma and Kansas, and in 1920 he rejoined the Empire Gas & Fuel Co. in the capacity of district geologist in Oklahoma. In September of 1921 he began his association with the Houston Oil Co. of Texas. He was district manager for the company in the Mid-Continent area until 1932 when he was transferred to the head office at Houston, where he became superintendent of the land and lease department in 1934 and was elected a director of the company in 1941. In these capacities, and also as petroleum engineer for the company, he keeps in intimate touch with all phases of field activity and with the regulation of the industry by State and Federal agencies.

Jan 1, 1943

By W. J. O'CONNOR

THE production of lead in the United States for the period from 1720 to 1912 was 10,432,668 tons valued at $924,600,000. The average price during this period was 4.4c. a pound, although lead sold at times below 3 cents. We know that in the early days of lead smelting in Montana lead was deliberately lost in the slag and only enough reduced as bullion to collect the silver. This bullion was freighted by ox team to Corinne, Utah, the terminus of the railroad at that time, and shipped to Swansea or Omaha, Neb., for refining. The slag from some of the above mentioned operations contained as much as 15 per cent lead and has since been resmelted. Since 1921 the production of lead has increased each year and the price and tonnage have been as follows :

Jan 1, 1926

By Charles L. Elliot

Data on mining applications of geophysical activity in the Free World in 1964 have been made available to SME again this year by the Society of Exploration Geophysicists. Worldwide data were collected as part of an annual service to the mining industry by the Committee for Geophysical Activity of SEG. Data are taken from 245 voluntary responses (53%) to questionnaires circulated to 463 company, government and university organizations engaged in mining geophysical operations and research all over the world. WORLD ACTIVITY Worldwide manpower utilization totalled 9323 professional man-months and $14.5 million was reported spent in mining geophysical activity in 1964. This is up from 9078 man-months and $12.6 million in 1963 and 8065 man-months and $12.8 million in 1962. Worldwide geophysical activity in terms of manpower utilization and expenditures is presented in the accompanying table.

Jan 9, 1965

By E. DeGolyer

WAR has wrought sharp and sudden changes in the pattern of the oil industry. The most obvious and most striking of such changes have been in the fields of transportation and refining. A third of the world's total oil production formerly started to market, tanker-borne, over the waters of the Gulf and Caribbean. Most of this oil went to our North Atlantic ports, supply points for the world's greatest consuming center. This tremendous traffic, disrupted by the loss of tankers as a result of requisition for military purposes and by the activity of enemy submarines, has had to be substituted largely by such lines of supply as could be improvised without loss of too much time. No single solution for this gigantic problem has been found nor is it likely to be entirely solved for some time to come. It has been solved in part, however, by rearrangement, reversals, and patching up of existing pipe-line systems; by overland transport of crude and products in tank cars on a scale never before attempted; by barging over inland waterways; and through the construction at long last of the "big-inch" line, the first leg of which is just being put into operation as far as Norris City, III. The tank-car traffic alone, reaching a peak of deliveries of 856,710 barrels per day into District 1 during the week ending Sept. 19, 1942, and accomplished at an expense of millions of dollars in extraordinary transportation costs, defrayed by the Defense Supply Corp. and by the mobilization of tank cars from all over the nation, is a story worth the telling but by some of those who directed it.

Jan 1, 1943

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.' In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By R. S. Wagner, R. G. Treuting, W. C. Ellis

Use of the Weisseizbevg goniometer for the study of the morphology of whisker crystals and transfer of the results to a stereograplzic projection are described. While in almost all instances a complete and rapid solution is obtained with a purely gaphical treatment, an absolute analytical treatment applicable to difficult cases is given. Examples are given for determination of growth direction and external features of a crystal, for detection of 'twintzittg, and for establislting the orientation relntionships in a kinked whisker crystal. We give here a method for the use of the Weissen-berg goniometerl" in the study of orientation relationships in "whisker" (micro) crystals3-8 and direct transference of the data to the stereographic projection. The operations are straightforward and require no involved calculations: in almost all cases solely graphical treatment is adequate. In a few complex instances, a more exact analytic method may be required. In the method, not only are equatorial reflections of an oscillation photograph used, but also those on higher layer lines, or those not occurring on a recognized layer line. Such reflections off the zero level are often essentialy to detect the presence of twinning. The method is particularly suitable for examination of whisker crystals since the axial or growth direction is almost always one of high symmetry, permitting a more restricted oscillation range to obtain the necessary reflections and an accordingly shorter exposure time. The method is also applicable when there is no lattice-related external symmetry, and is as well able to identify external crystal surfaces, when such exist, with the aid of an optical beam. Thus growth direction, identification of lateral faces, twinning, and orientation relationships in a kinked crystal can be established. A test for the Eshelby twist6-8 can readily be made. The method can be used for orientation, for structure analysis, and as an aid in the identification of an unknown crystal. Moving-film techniques have previously been employed variously for crystal-orientation studies.1,2,9-13 In particular, use of the Weissenberg method for orientation determination has been reported by Wooster and wooster.14 While their method derives the same data as here described, it differs in depending on the tracing of constant p streaks, a less than dependable phenomenon with small specimens, a few microns or less in cross section. The Laue method can and has been used for orientation studies of microcrystals,15 e.g., 2 p in cross section, but requires the extreme intensity and concentration from a microfocus tube to obtain reasonable exposure time. PRINCIPLES OF THE PRESENT METHOD Consider a crystal of random orientation with respect to the oscillation axis in a Weissenberg goniometer. Its diffraction pattern need not necessarily result in recognizable layer lines. In Fig. 1, a stereo-graphic projection of the reference sphere is given with the equatorial plane XZ normal to the oscillation axis Y, and the X-ray beam directed from X towards 2. The great circle ZZ is then normal to the beam, and the axes are right-handed. Thus the reflected X-ray beam lies at the intersection R of small circle ARB of radius 28 from 2, and of small circle RE of radius a from the rotation axis Y. a is the conventional semiapex angle of a cone of diffracted rays from the atoms aligned in the direction

Jan 1, 1967

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By W. C. Hagel, H. J. Beattie

Phases present at 2200° and 1500°F (1204° and 816°C) were identified in sixty wrought developmental austenitic alloys possessing wide compositional variations. The bases were iron-, cobalt-, and nickel-rich as well as a base with equal parts of each. There are only two structure types previously not found in similar alloys, viz .-the Co3 W and the Fe3Al types. A molybdenum-rich monocarbide decorates dislocations with unusual clarity. Other results provide correlations between alloy composition and phas e precipitation. Grouping intermetal -lic phases into three general classes : I) geometrically close-packed, 2) topologically close-packed, and 3) bcc derivatives, the nickel base prefers the first, the iron base the second, and the cobalt base the third—each base tending to shun the other two classes. Thus, a crystal-chemistry effect previously noted by Laves and Wallbaum can he expanded for these Group VIII elemental bases. There appear to he no quaternary or higher -order structure types requiring more than three atomic species. AFTER studying aging reactions in many diverse commercial austenitic alloys1-4 as a function of detailed time-temperature variations in heat treatment, it became apparent that matrix composition influenced structure types and morphologies to a large extent. These tendencies were related4 to a crystal-chemistry effect uncovered by Laves and Wallbaum.5,6 We have now directed our efforts to exploration of the whole ternary field, covering the standard base elements—iron, cobalt. and nickel— with 10 to 20 pct Cr and moderate amounts, up to 10 pct, of the usual alloy additions. Solutioning and aging treatments were held constant with major emphasis on X-ray identification of microconstituents. The possible existence of exceptions to the Laves-Wallbaum effect, or any new phases, was sought. Phases appearing in austenitic alloys can be classified as geometrically close-packed (gcp), octahedral or nonoctahedral interstitial compounds, topologically close-packed (tcp), semicarbides, and bcc derivatives. Crystal structures of the first four classifications can be visualized as a dense packing of semirigid spheres of different sizes, while the bcc derivatives represent a less efficient packing of spheres. The Laves-Wallbaum effect involves the gcp and tcp phases. Gcp phases possess both tetrahedral and large octahedral interstices; examples are Ni3Ti(n), NiSAl(y'), Co3W(E), and other ordered AB3 compounds where B atoms are smaller than A. Their precipitation is primarily intragranular, presumably coherent with an austenitic matrix, and a chief source of strengthening. Most octahedral interstitial compounds (e.g., CbC, Tic, TiN, Mo2C) have a gcp lattice of large metal atoms which accommodate small carbon or nitrogen atoms in the octahedral interstices. The compound Ti2SC, previously designated Y phase or T phase, can, with some reservation due to its partial co-valency, be placed in this category.7 The nonoctahedral interstitials (e.g., M7C3, Fe3C) represent close-packings of spheres in structures that provide larger triangular-prism interstices for carbon, since the octahedral interstices formed by chromium and iron atoms are too small. Tcp phases possess only tetrahedral interstices; examples are Laves (Fe2Ti, Fe2Cb, Fe2W...AB2), p(Fe7MO6, Co7W8.... A8B7), and (FeCr, Co2Cr3)

Jan 1, 1965

By George P. Chapman

Mica is a platy mineral occurring in a variety of complex hydrous aluminosilicate forms with differing chemical composition and physical properties. Principal minerals in the mica group include: Muscovite-potassium mica (colorless or pale green/ ruby) Phlogopite-magnesium mica (dark brown or amber) Biotite-magnesium-iron mica (black or dark green) Lepidolite-lithium mica (lilac) Selected properties are given in Table 1. Muscovite is most important commercially with phlogopite of lesser use. The laminated structure of mica enables it to be split into very thin films which are transparent and tough as well as having outstanding dielectric and insulating properties. Commercially, mica is used in a number of forms (Chowdbury, 1941; Rajgarhia, 1951; Skow, 1962). Sheet mica consists of flat sheets mined from naturally occurring books of mica, free from defects and capable of being punched or stamped into required shapes. Sheet mica is separately classified into blocks, films, or splittings according to thickness. Built-up mica, or micanite, is made by arranging overlapping splittings in layers , cemented with a binder and pressed together at high temperature. Reconstituted mica, or mica paper, is made by depositing fine flakes of high-quality scrap mica in a continuous film impregnated with binder. Scrap and flake mica are normally unsuitable in quality or size for making sheet mica. Originally the term scrap mica referred to the waste byproduct of mining and fabricating sheet mica, and distinct uses were developed for this material. Subsequently it became economically feasible to mine lower quality mica for these uses, and the term flake mica was introduced. Although the two terms are still used somewhat synonymously, it is considered better, at least in the United States, to use the term flake mica in referring to mica mined for uses other than as sheet mica; and to restrict the term scrap mica to mica mined for or with sheet mica, but which will not meet the specifications. Synthetic mica, such as fluorophlogopite, is produced by slow crystallization of a melted blend of pure raw materials. Mineralogy In the true sense the term mica does not relate to, a particular mineral, but to a group or family of minerals of similar chemical composition and to some extent similar physical properties. These minerals are predominantly potassium aluminum silicates with varying amounts of magnesium, iron, and lithium. The precise formulas and isomorphic relationships of the various group members have been studied, but general agreement has not been reached (Grimshaw, 1971; Hurlbut, 1952; Skow, 1962). The general formula describing the chemical composition of micas is [X2Y4-6Z8020(OH, F)4, where X is mainly K, Na, or Ca; Y is mainly Al, Mg, or Fe; Z is mainly Si or Al (Deer, et al., 1962).] These minerals have an internal structure of the layered lattice type where the silicon atoms are in the center of a tetrahedral grouping of oxygen atoms. The groups are linked together in a single plane by three oxygen atoms that lie within the common plane. Each of these oxygen atoms is shared by two tetrahedra. These linked tetrahedral groups, when continually extended, produce a hexagonal network within the plane. This internal structure of the mica has been used to explain the ex-

Jan 1, 1983

By L. G. Jones

An approximate method of calculation is developed in this paper which allows duplication of radial unsteady-state gas flow computer results where Darcy's law applies, such as those reported by Aronofsky and Jenkins and Bruce, Peaceman, Rachford, and Rice. Moreover, the new calculation method can be used to obtain results for radial unsteady-state gas flow obeying the quadratic flow law proposed by Duwez and Green. Means are discussed for predicting well behavior at single or superimposed flow rates in finite or infinite reservoirs, determining reservoir rock properties from well-test data, reproducing and interpreting back-pressure test data, and determining the radial extent and reserves of gas reservoirs from well-test data. Example calculations are presented for gas flow following both Darcy's law and the quadratic flow law. INTRODUCTION Since the publishing of U. S. Bureau of Mines Monograph 7,1 most gas-well testing methods have been based on the equation q = y (pl2 - pw2)a, where q = production rate, pl and pw, are formation pressure and sandface pressure, respectively, and y and a are constants to be obtained from test data. These methods, used for predicting both deliverability and "open-flow" capacity of gas wells, have been useful and accurate in many cases but unsatisfactory in others. Even at best, however, they do not supply information about the formation or lead to an understanding of nonsteady-state gas flow in porous media. Many theoretically based studies2-4 of gas flow obeying Darcy's law have been made.' Since the partial differential equations which result from combining Darcy's flow law with the continuity equation are nonlinear, most of the published research consists of either numerical solutions or analytical solutions for linear approximating equations. Such solutions have been of limited value in field work due to their unhandy form and their failure to correlate most field data. There is evidence5,6 which indicates that Darcy's law is inadequate to describe gas flow at some flow rates of practical interest. A quadratic flow law: which reduces to Darcy's law at low rates, is more successful in accounting for experimentally observed behavior. This flow law has been applied successfully to a few hypothetical reservoir cases in work which has recently been published.10 However, these numerical solutions of the equations involved have been successful only on a special analog computer. Routine applications to field cases would be awkward and have not been attempted. The present paper describes an approximate method for computing nonsteady-state gas flow solutions which has been completely successful in predicting the results for both Darcy flow and quadratic flow obtained by elaborate numerical methods. The new calculation method allows determination of the observable variables in gas-well testing at constant rates. It is similar to the scheme of using a succession of steady states suggested by Muskat7 in that it makes use of steady-state and material-balance equations. It also is similar to the work of Aronofsky and Jenkins2 in that the new method includes Aronofsky and Jenkins' stabilized flow equation as a special case. It improves upon both of these calculation schemes in that it accurately describes all portions of reservoir history and suggests means of determining reservoir rock properties from well-test data. This paper deals only with production from a reservoir, in which case the rate is defined as being negative. The reservoir studied here is a homogeneous, disk-shaped porous body of uniform thickness, with all boundaries sealed except the inner radial boundary of the well.

By P. S. Roller

P. S. ROLLER,*College Park, Md.-The author introduces the idea of a grind limit, or lower size limit of the particles formed directly by grinding, and this is stipulated to be 0.70 micron. I wonder where all the particles come from that lie between the resolving power of the microscope and 0.7 micron, which are seen under a microscope in examining a sample of grind? There is also introduced the idea of excess fines; this is all right in itself but the author's quantitative definition seems to be virtually impossible to justify, and, moreover, is obscure. Just why E, the excess fines, should he defined as the distance between an F line and a y line is hard to follow, and just where the distance should be measured does not appear to be stated, as it should be since the F and y lines intersect and the distance between will depend upon where that distance is measured. The basis of the presentation is the relation of log weight against log size that was "discovered" by Schuhmann. While this relation is implied to fit, the only evidence that I can see is a slightly irregular line in Fig. x between 2 per cent and 18 per cent by weight and then a precipitous drop at 18 per cent away from any sort of straight line. Some of the conclusions are rather startling. It is stated that E, the excess fines, remains constant for all the comminution products of any particular material, except that it may decrease for some coarse crusher products. No reason is given for this assertion. One would, on the contrary, expect that excess fines, if such a concept is permissible, would generally vary with different conditions instead of being constant. Again, "as much net energy is required to reduce a ton of quartz to particles of the grind-limit diameter (namely, of course, 0.7 micron) by grinding as is required to melt the quartz." This would require many data to prove, but no proof is given; any consideration would reveal the impossibility of such a result. Still further, ore samples "ground to widely different sizes, and with different circulating loads and different size distributions or product, show the same production of new surface area per revolution of the mill, when this grind limit is used." This statement is confuted by ordinary experience, which teaches that grinding efficiency varies generally with the condition of material. For example, the cushioning effect of fines is widely accepted, while the inefficiency of a ball mill when the feed is too coarse is also well known. R. SCHUHMANN, JR.," Cambridge, Mass. Contrary to Mr. Bond's stand, there is a great deal of miscellaneous experimental evidence that comminution does not stop at around 0.7 micron, nor does it cease consuming energy at that point. Comminution is in fact recognized as an important method of producing colloids., Mechanical comminution methods were used by von Weimarn6 to produce colloidal dispersions of a variety of solids, including the minerals chalcocite, galena, hematite, stibnite. Utzino7 gives average particle sizes ranging from 0.02 to 0.09 micron for colloids produced by mechanical comminution of several crystalline solids. Andreasen and Berg' have ground

Jan 1, 1941

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.' That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes' developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C' is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.', ' " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann's size modulus has been found convenient.' Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-' dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J'-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-'dx\

Jan 1, 1960

By R. T. DeHoff

Saltykov's meihod for the determination of the size distribution of spherical particles from measurements made on random plane sections is extended to particle shapes which are not equiaxed. The analysis permits the deterrrzination of the size distribution of aggregates of ellipsoidol particles provided all particles have tlze same shape. V ARIOUS solutions to the problem of the determination of the size distribution of spherical particles from measurements made on random plane sections have appeared in the literature since the original solution was first published by Scheill in 1934. Solutions have been offered utilizing measurements of the diameter1y2 or area3'4 of circular sections that result when a test plane is passed through an aggregate of spherical particles, and the length of intercept5y6 that results when a test line is passed through the aggregate. To the best of the knowledge of the author, no method has been proposed which permits the determination of the size distribution of particles that are not equiaxed. The purpose of this paper is to develop a method which permits the determination of the size distribution for a specific class of particle shapes which cover awide range of axial ratios; namely, ellipsoids of revolution. In the interests of simplicity, it is necessary to limit consideration to aggregates of particles which are all similar in shape; that is, the ellipses which, by rotation about one of their axes, generate the particles, all have the same axial ratio. The size distribution, which is to be determined by the analysis, is arbitrary. It is also assumed that the section, or sections, upon which the measurements are made represent the average of all possible sections through the structure. This ideal condition can be approached as nearly as may be desired by observing a sufficient area of sections taken at random positions in a randomly oriented aggregate, and in random positions and orientations in an aggregate that has one or more axes of orientation. SIZE DISTRIBUTION FOR PROLATE ELLIPSOIDS Consider an aggregate of cigar shaped, geometrically similar particles (prolate ellipsoids), dispersed in an opaque matrix. Let the size of each particle be specified by the length of its minor axis, By Fig. 1, and the shape, q, be defined by the ratio of its minor to its major axis, B/A. Let the index, j, refer to dimensions of ellipsoids in a particular size class, and the index, i, to dimensions of an ellipse resulting from the intersection of a test plane and a particle. The size of such a section is specified by the length of its minor axis, b. Let the particles be arbitrarily divided into k size classes, and let the increment of size between each class be A, where A = &,$, B,,,being the minor axis of the ellipsoids in the largest size class. Since all sections are represented on the test plane, the minor axis of the largest of the sections observed, results from the intersection of the test plane with an ellipsoid in the largest size class at its center, and is therefore equal to Bmax Thus the increment, A = The final result will consist of the k numbers which represent the number of particles in each size class per unit volume of aggregate:

Jan 1, 1962