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By N. A. D. Parlee, N. M. El Tayeb

Fe-V alloys with small percentages of vanadium show no deviations from Sieverts' Law up to P~, = 1 atm in the 1600º to 1750ºC region. At somewhat under 8 pct V and up to at least 20pct V, at 1604" and 1661 °C, nitrogen absorption follows Sieverts' Law at low Pn2 values, but deviates from this law beyond critical values of pn2, due to formation of a nitrzde phase of approximately VN composition. The behavior below these solubility limits can be described at all temperatures by the equations: RAO and parlee1 suggested that the nitrogen absorption curve for liquid iron alloys takes the general form shown in Fig. 1 when an alloy nitride precipitate is formed. They showed that the precipitation of 6 titanium nitride from liquid Fe-Ti alloys follows this general scheme and dealt with the general theory involved. Recently, Evans and Pehlke2 reported their research on the precipitation of aluminum nitride from liquid Fe-A1 alloys. Fountain and Chipman's recent paper3 on the precipitation of boron nitride from solid solution contains a fine example of the analogous behavior which they have been studying in the solid state. Researches on the absorption of nitrogen by liquid Fe-V alloys have been described by various authors.1,4-7 Most of this work has been confined to fairly low vanadium concentrations and rather high temperatures because of difficulties variously described as, formation of surface scums, bridging, and so forth. This behavior and the rough thermo- dynamic calculations made by chipman,8 over eleven years ago, indicated that excessively high vanadium concentrations should not be required for vanadium nitride precipitation. It seemed desirable to look for and study this precipitation in order to fill out the thermodynamically interesting nitrogen absorption data on these alloys. EXPERIMENTAL METHOD The general method used was essentially the same as employed by Rao and parlee,1 in which a Sieverts type of apparatus was used and the precipitation of the nitride detected by the "break-point" in the Sieverts' Law line, and by the visual observation of the formation of the new phase on the surface of the melt. There were, however, a few differences in apparatus and technique as described below. The oil manometer used by Rao and parlee' to measure low partial pressures of nitrogen was not employed. The present authors sought to avoid as much as possible the exposure of the liquid alloy to low total pressures of gas during the 6 to 10 hr long runs because of the heavy iron evaporation-loss errors involved. This was achieved, partly by keeping evacuation times to a minimum with fast pumping but largely by the use of two burettes, one for argon and one for nitrogen, and using them to equilibrate the alloy with mixtures of argon and nitrogen rather than nitrogen alone. Each run involved a careful sequence of operations. After melting, de-

Jan 1, 1963

By L. L. McMurray

ILMENITE is the most important raw material for manufacture of titanium dioxide.1 Industrially, several other products are made from ilmenite, the most important of which are: ferrotitanium, ferro carbon-titanium, copper-titanium, titanium carbide and titanium nitride. The production of titanium metal is still in the laboratory stage because of the difficulty of extraction and as yet no important application for the metal has been found. Ilmenite has received considerable attention as an industrial raw material. Imports of ilmenite concentrates for the first nine months of 1941 were 156,737 short tons, the chief source being Travancore, India.2 Domestic production of ilmenite has here-tofore been confined to Amherst and Nelson Counties, Virginia, where a complex rutile, ilmenite, and apatite ore is mined and treated to utilize all three of these minerals. A recent report3 has described development of the large titaniferous magnetite ore body at Tahawas, New York, where it is expected that 800 tons of ilmenite concentrates, containing 48 per cent Ti02 will be produced daily. Additional domestic production is expected from a large ilmenite deposit recently opened in Caldwell County, North Carolina. Flotation tests indicate that a high-grade concentrate containing 53 per cent Ti02 can be made from the North Carolina ore. Prospecting of domestic ores in other areas has been reported.4 It appears that increased domestic production of ilmenite may well save considerable shipping space so vitally needed in these times. The composition and chemical structure of pure ilmenite is given by Dana as: FeO, TiO2; Ti, 31.6 per cent, Fe, 36.8 per cent, 02, 31.6 per cent. This composition is variable in that some iron or titanium may be replaced, giving a variable iron-titanium ratio. As an example, the iron-titanium weight ratio of ilmenite in Caldwell County, North Carolina, has been determined to be 0.94 (using 97.1 per cent ilmenite concentrate obtained by heavy liquids on minus 150-mesh ore) compared with theoretical 1.16. No rutile was noted in this ore to account for the low value. This North Carolina ore is free of magnetite, which is a common associate of ilmenite ores. In view of a large potential production from North Carolina, the Tennessee Valley Authority conducted a study of methods of concentration of that ore, of which the results are reported herein. THE ORE Five samples of ore were taken from the deposit at various exposed locations and were mixed for the study and testing. An attempt was made to proportion the amount of weathered and unweathered portions in making the composite sample, so as to approximate actual operating conditions. An examination of representative specimens of the sample showed the following general facts: I. The black mineral comprising nearly 70 per cent of the ore is ilmenite.

Jan 1, 1944

By R. W. Shoenberger, J. A. Grina, R. J. VanPelt

The many alternatives open to coke plant operators for improving overall coke quality and strength are discussed in this paper. Programs undertaken by US Steel research and coal operations during the previous ten years to improve coke strength are described. New techniques in use, or being considered for future use, are also discussed.

Jan 1, 1982

By E. O. Wagner, V. F. Parry, W. S. Landers

Development work has shown that the yield of primary tar from coal is proportional to the heat in the volatile matter of the coal and that the yield of tar from noncoking coals may vary from 10 to 45 gal per ton on the ash-free and moisture-free basis. Pilot plant operations have proved that 100 to 135 pct of the bench-scale carbonization-assay yield of tar can be obtained. FOLLOWING investigations by the Denver Bureau of Mines on drying fine coal in the entrained state,'. ' Texas Power & Light Co. employed the fluidized technique to upgrade Texas lignite for use in power plants. Because of the rapidly rising cost of natural gas in Texas the company agreed to cooperate with the Bureau of Mines in studying further the upgrading of lignite by low-temperature carbonization, since potential value of the tar would help offset the cost of fuel. Considerable interest was aroused, therefore, when Aluminum Co. of America decided to use dried lignite in its 240,000-kw power plant at Rockdale, Texas, operated by Texas Power & Light. Carbonization of coal before burning in a power plant is not new. Plants in Germany have been operated for many years on carbonized brown coal and lignite briquets produced in large integrated plants. Large-scale experiments in carbonizing pulverized coal with hot flue gases were made 30 years ago at Milwaukee," and many inventors have proposed other processes. In the U. S., technical and economic problems have prevented successful operation of large plants on carbonized coal. but new techniques of handling solids in fluidized beds may overcome these difficulties, particularly if the higher volatile noncoking coals are used. Any bituminous material will decompose when heated to about 900°F to yield primary tar, gas, and char. The quantity of tar obtained from various coals depends on their rank and volatile content and to some extent on rate and method of heating. The liquid products derived from thermal decomposition of peat, brown coal. lignites, oil shale, and noncoking bituminous coals can be easily liberated by rapidly heating these materials in a fluidized bed at about 500°C (932°F). Since it takes only a few minutes to heat small particles of fuel to carbonizing temperature in a fluidized bed, processing plants can be built to handle up to 50 tph at relatively low cost. The pioneering development work being conducted at Rockdale, Texas, by Alcoa and Texas Power & Light will solve many engineering problems of such operations. The Bureau of Mines at Denver has studied the carbonizing properties of several hundred coals by small scale assay at 500°C, deriving a simple correlation between the potential yield of tar and the proximate analysis. This correlation, shown in Fig. 1, compares the heat in the volatile matter of the coal with the potential yield of primary tar. The yield of primary tar varies from 12 to 50 gal per ton of pure coal." About the same amount of heat is needed to * MAF equals moisture-and-ash-free basis. distil any dry coal at 500°C, and the time required to carbonize a given particle size is about the same for any coal. It is therefore obvious that coals rich in volatile matter will show the greatest profits when processed. Texas lignites are rich in volatile matter, which contributes some 5700 Btu per lb of MAF coal, and the potential primary tar and oil yield from this lignite averages 12 pct by weight or 27 gal per ton from the pure lignite. Texas lignites are considerably richer in potential tar than lignites of North Dakota and Montana. During 1950 the Bureau of Mines conducted many experiments on carbonizing fine dry coal in the entrained state, publishing a report4 n major features of pilot and commercial-size units required to carry out the process. Additional experimental work has been done at Denver and the pilot plant has been improved, particularly the facilities for studying removal of fine dusts from tar vapors and gases at high temperatures by electrostatic precipitation. A number of materials have been carbonized, including sawdust, peat, brown coal, Brazilian oil shale, lignites, and the lower rank bituminous coals having noncoking properties. Straight coking coals cannot

Jan 1, 1957

By C. A. Doh, R. Q. Fields, M. Lebourg

A formation tester run on logging cable is now available to the oil industry. It offers a method of safely and rapidly testing possible producing formations in uncased holes. These tests can be made up the hole after running the electric log. Reservoir pressure data is continuously recorded at the surface as the fluid sample is extracted. The tester may be assembled with a reservoir of 1-, 2.75-, or 5.5-gal capacity. A retaining pad on the body of the tool is expanded against the wall of the hole at the exact depth desired; this depth is determined by electrical log control. Two bullets are then fired through the center of the retaining pad which create a connection between the formation and a flow line to the sample chamber. When the chamber is filled, a valve is closed and the fluid sample sealed at maximum pressure. The tool is retracted to minimum diameter and brought out of the hole. Electrical circuits permit a complete recording at the surface of the mechanical operations of the tool as well as the formation pressure build-up and the hydrostatic mud pressure. The tool was introduced commercially during the latter part of 1955 in the Gulf Coasts of Louisiana and Texas. Over 1,000 operations have been made to date (Sept. 1, 1956); 50 per cent of which resulted in successful tests. Failures have been due mostly to ineffective sealing in unconsolidated sands. One major company had 41 successful tests out of 80 attempts with 23 ineffective pad seals. Results for this company were very gratifying as to pinpointing gas-oil ratios, indicating productive permeabilities and aiding in determination of fluid content where electrical log and side-wall coring information were inconclusive. Eight typical pressure curves are discussed (including misruns). Six types of fluid recoveries are interpreted. Eight actual field examples of electric logs, showing the problems solved by the formation tester, are illustrated. The present applications of the tool are discussed: 1. Determination of productive fluid—varticularlv differentiating between gas and oil. 2. Determination of reservoir pressure as an aid to: (a) safety in completion technique, (b) reduction in drilling costs, and (c) reservoir analysis. 3. Determination of minimum gas-oil ratios. 4. Location of gas-oil or oil-water contacts. 5. Recovery of samples for examination and analysis: oil (gravity); gas (hydrocarbon content); water (salinity). Additional applications envisioned for the future are also given: (I) subsurface exploration based on accurate pressure, (2) recovery of fluid samples from the undisturbed reservoir for PVT work, and (3) possible quantitative study of permeabilities or productivity index. Running the formation tester requires no special pre-cautionary measures. Because full hydrostatic mud pressure is maintained at all times, well depth is no problem. Thus, the method allows safe, economical testing in wells which heretofore could only be tested by setting casing. INTRODUCTION A new method of safely and rapidly testing possible producing formations in uncased holes is achieving considerable success. The method offers promise of further advances in reservoir study. Called the formation tester, the new instrument is unique in that it operates on logging cable. It thus offers all the advantages of wire-line operations and becomes an important adjunct to present logging and side-wall coring services. The tester is operated against the wall of the hole at any depth desired. Zones to be tested are usually determined by a study of the electrical and the micro-caliper surveys. Reservoir data, as well as the operating cycle of the tool in the hole, are continuously recorded at the surface during the operation. The tester, as it was originally designed, was capable of recovering a 1-gal sample of reservoir fluid per trip in the hole. Tools with reservoirs of 2.75- and 5.5-gal capacity are now available. The 5.5-gal reservoir is equipped with a segregating system, set before going in the hole, so that the last portion of the recovery (usually 1 gal) is automatically separated from the first portion. This makes it possible

Jan 1, 1958

By T. O. Anderson, E. J. Stahl

Tests to increase knowledge concerning the process of hydraulic fracturing have been performed on three wells in the Allegheny field in western New York. The fracture orientation and its physical appearance at the well-bore was determined by impression packers run at appropriate times throughout the program. Fract~tre azi171uth and its dimensions thus determined were compared to the rock properties and treatment conditions. Logs to provide data concerning rock properties and to improve identification of vertical fractures were run before each step of the fracture treatment. Pressure osc~illu~iot~s were studied after each phase of tile treatments surface pressures during treatment. These measurements show that subsurface pressures exhibit many of the same characteristics as surface pressures during treatment of a well; however, transient pressures are dampened and deelayed in time at the bottom of the well when COmpared with surface pressures. Data obtained from this study provides a means to help locale and determine orientation of vertical fractures made in the open wellbore. Although these rests were performed in only one area, much of the information gained may be applied to fracturing programs in orher areas. INTRODUCTION In this study, various tests were made to provide data to better understand formation fracturing in situ. The reservoir studied is the Richburg oil sand which is a part of a series of predominantly grey sandstones and shales with occasional brown sandstone layers, known as the Caneadea unit of the Canadaway group of Upper Devonian age. Average physical characteristics of 12 cored wells in this area are 13-ft thick gross sand formation, 12-ft thick net sand. 1.7 md permeability, 11 percent porosity, 44 percent oil saturation (before secondary recovery) and 16 percent water saturation (before secondary recovery). This particular area of the Allegheny oil field was originally drilled prior to 1890. The first waterflood secondary recovery attempt was made in 1929. The present sustained waterflood development began in 1951 and is being carried out on a 4.5 to 5-acre spacing. Objectives of these tests were to (I) study fracture azimuth and dimension in relation to rock properties and treating conditions, (2) improve fracture identification techniques, (3) compare surface and subsurface pressure during all phases of treatment and (4) compare the periods of the fluid column oscillations occurring after each phase of treatment. Although the areas of investigation listed appear divergent in purpose, the program was designed primarily to increase knowledge of down-hole conditions leading to rock failure and extension of the fracture thus created. TEST PROCEDURES Wells upon which tests were conducted are designated as Wells 1 through 3. Well 2 was located 440 ft north of Well 1, and Well 3 was located approximately 880 ft west of Well 1. Wells 1 and 2 were completed with cable tools, while the producing interval of Well 3 was rotary cored using fresh water as the drilling fluid to obtain oriented cores. Tests were divided into separate phases on each well as the fracturing program progressed and consisted of measurements performed prior to treatment, during and after the formation breakdown operation. during fracture treatment and after treatment. To verify location and azimuth of the fracture created, and to obtain an impression of wellbore irregularities, a packer was used (Fig. 1). This packer was lowered on tubing into the wellbore opposite the interval under study and inflated in stages to allow the impression material to conform to the wall of the wellbore. A magnetic compass was attached to the tool for orientation reference. Impressions made prior to treatment showed no existing fractures in the wells under study. Impressions made after both formation breakdown and treatment pro-

By F. Bonaccorso, G. Venturello, C. Antonione

A study of the effect of small amounts of interstitial impurities on recovery and re crystallization in high-purity iron (99.995 pct) has been undertaken. This paper gives results on the effect of carbon, introduced in small-dosed amounts @om 0.0005 to 0.0086 wt pct) by heating iron specimens of high purity m a static atmosphere of CO + ,. The materials prepared in this way, cold-worked 80 pct and subjected to a series of isochronal and isothermal annealings, were submitted to examinations by X-rays, micrographs, and hardness tests. It was observed that effect of carbon is remarkable in the sense of blocking recovery of mechanical properties up to the temperature at which re crystallization begins. On the contrary, carbon has a negligible effect on primary re crystallization temperature, when compared with the known effect of substitutional impurities. This is in agreement with the high mobility of interstitials. In effect, only a slight decrease, -20 pct, of the grain-boundary motion rate was noted, due to the interaction between the grain boundary and the carbon atoms. On the other hand, in the samples in which the carbon content is above the solubility limit at the temperature at which re crystallization occurs, a slight increase of nucleation frequency is noted due to the presence of precipitated carbides. ThE effect of purity on recovery and recrystalli-zation phenomena has been known for a long time; however, recently, new attention has been given to the problem since new methods for obtaining metals with extremely low impurity contents have become available. Most of this research work essentially concerns the effects of impurities which cause precipitates or give rise to substitutional solid solutions. The works of Bolling and winegard1 and Aust and utter' on lead, and Vandermeer and orddon' on aluminum, 01sen4 on nickel, and Abrahamson and Blakeney on iron should in particular be referred to. On the effect of this type of impurities a quantitative theory has been formulated by Detert and Lucke6 and has lately been discussed critically by Cahn7 and Gordon and vandermeer.' Interstitial solid solutions in iron have not as yet been studied. As the study of the effect of interstitials is of great interest both from a theoretical and practical standpoint, it was deemed useful to examine the effects of carbon, nitrogen, and boron on recovery and primary recrystallization of iron. There already is some work by Chaudron et al.,1-" on the effect of interstitials on iron; their work, however, mainly concerns secondary recrystallization. The present paper refers in particular to the effect of carbon. EXPERIMENTAL PART Preparation of Materials. The pure iron used for this research was obtained from FeCIS recrystal-lized and purified by extraction with isopropylic ether. From the ferric chloride purified in this manner, hydroxide was precipitated with a solution of very pure ammonia, and, by calcination in pure sintered alumina crucibles, oxide was obtained. Reduction of the oxide to iron sponge was performed in sintered alumina tubes with very pure hydrogen at 650°C; at the end of the operation temperature was increased to 900°C. Specimens for the experiments were obtained by sintering the sponge at 1480°C in pure Hz after a pre sinter ing treatment at 900° C. It is important to note that the treatment at 1480°C in Ha produces a further purification from more volatile elements such as zinc, cadmium, arsenic, lead, and tin. Details on the preparation and characteristics of this type of very pure iron are given in a previous work.'' Only the complete analysis performed by neutron-activation methodsz3 is given here, Table I. Some of the specimens prepared in this way were carburized in the 0 region with very low amounts of carbon by treating them at 700°C in a static atmosphere of Ha containing a definite amount of CO. The set-up used is described in Fig. 1. A gas-tight quartz tube containing the specimen to be carburized and an internal friction control specimen, after being evacuated, was filled with Hz

Jan 1, 1963

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer's organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By E. H. Kelton, R. D. Grissinger

In designing structural members of steel and some other materials the design engineer has available recognized values of elastic modulus and safe working stress that may be substituted in well-known engineering formulas to give him desired cross-sectional areas and deflections for a particular part. Zinc, on the other hand, has no generally recognized modulus. It flows under continuously applied loads. Therefore, the designer of structural members must use a range of working stresses depending on the continuous load and the amount of permissible distortion. The only method of obtaining these values is by creep testing. Creep testing of zinc has been carried on for some 20 years by this laboratory, covering a wide range of zinc and zinc alloys. Types of test included tension, compression, and simple and cantilever beams at temperatures ranging from o to I50°C. Specimen conditions ranged from as-cast or as-rolled to accelerated aged in steam or dry air. Effects of plating were investigated also. It is not the intention of this paper to expound all these factors but rather to present the final data on well-known zinc die-casting alloys and to suggest means of applying these data to engineering design. Early Work In the early work on creep testing of zinc, the direct-loading tension method was used. However, direct loading of die castings was unsatisfactory because of the high loads required. For instance, a standard die-cast tension bar having a cross-sectional area of about 0.049 sq. in. would require a direct load of about 1000 lb. for a unit stress of 20,000 lb. per sq. in. Also, tests were made at nominal room temperature, but normal variations caused fluctuations greater than those due to experimental error or other causes, so that control of this variable within ±1/2°C. seemed essential. These two factors led to the development of an apparatus described by J. Ruzicka,' in which the specimens were loaded by means of a lever and were held at constant temperature by means of an oil bath. While Ruzicka's apparatus yielded excellent check results, it seemed desirable to have some setup by which literally hundreds of die-cast specimens could be tested at the same time. This would permit the conducting of a number of low-load tests designed to run 10 years or longer and still leave capacity for current high-load work. Beam testing in a constant-temperature room was the answer. Test Method Preliminary work indicated that die-cast beams of various lengths and cross scctions yielded the same result within reasonable limits regardless of whether they were tested as simple beams, uniformly loaded beams, or cantilevers. Accordingly, the simplest type was adopted. This was a,

Jan 1, 1945

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company's technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By E. G. De Coriolis

THE development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent), the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out-namely, 2100° to 2150°F.-is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. "FIRELESS COOKER" PROCESS For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (1) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgeon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1945

By EVERETTE DE GOLYER

USE of geophysical methods in the search for new pools and as an aid in the development of known pools and prospects reached a new all-time peak for the oil industry in 1933. The outlook for 1934 is for work to continue at an even greater rate. The area of greatest activity, as in previous years, was in the Gulf coastal plain of Texas and Louisiana, particularly through a belt of territory some 20 to 30 miles wide parallel to the coast line and some 80 miles inland from it-the so-called "Jackson play" or "Conroe trend." This area was surveyed in an attempt to find additional pools of a type similar to Conroe, a pool not discovered directly as a result of geophysical surveys but one which was indicated by refraction surveys before it was drilled and one which was accurately outlined as to structure by reflection surveys shortly after the completion of the first few wells. Surveys were made over this belt, extending from Texas, across Louisiana and into Mississippi and Alabama, chiefly by the reflection method and torsion balance, and to some extent by pendulum and magnetic methods.

Jan 1, 1934

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By E. G. De Coriolis

The development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent). the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out—namely, 2100" to 2150°F.—is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. Fireless Cooker'' Process For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (I) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgcon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1949

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By L. G. Austin

If S (x) is the specific rate of breakage of size x and B (x, y) (see Table 1 for Nomenclature) is the cumulative breakage distribution function, the Herbst Fuerstenau2 assumption is that Inserting this assumption into first-order grinding equations it has been shown" that there are then simple analytical solutions to the grinding equations, as shown in Table 2. In this context "plug flow" is defined as all material passing through the mill in the same length of time, the residence time t. The term "n fully-mixed" means that the mill has a residence time distribution" which can be treated as if the mill were n equal fully mixed sections in series. In addition it has been shown that the assumption of Eq. 1 also leads to simple analytical solutions for closed-circuit, steady-state grinding with an ideal classifier at the mill exit returning oversize to the mill feed. The solutions are also given in Table 2, with µ as the ideal classifier cut size, C the circulation ratio, and Q (x) the size distribution of the circuit product. The specific surface area of these size distributions is where the density-shape factor k. is assumed to be constant with size. In practice, most methods of size analysis or area [ ] measurement have a finite lower limit, so that the integration is really performed from xm, to xm, For a realistic degree of grinding the value of So is dominated by the fine sizes because of the 1/x factor. Consider batch grinding of a feed of size y to y + dy. The batch grinding solution given in Table 2 is then [ ] The fresh surface area produced is the area of the fines plus the area of the original material remaining minus the area of the original material, [ ] Little error is introduced by neglecting the last term on the right-hand side since at t = 0 it is zero, and when t is significant the first term dominates because of the fine sizes produced. In addition, the form of P (x, t) for [ ] realistic values of S (x) 2t ax° is such that the major fraction of fresh surface produced is contained within the bottom 10% of weight of broken material, that is, for sizes for which P(x, t) < 0.1 (providing y is not near x.,). Thus for surface area purposes Eq. 3 can be approximated by [ ] becomes providing again that the feed sizes are coarse relative to xmi. Then the fresh area production is and W is the mass in the mill. The rate of surface production is WK, and the specific surface is Kt. From Table 2, the specific energy is mt/W so surface production per unit energy is [ ] Surface produced per unit energy input = KW/m (8) where m is the energy input of the mill. Clearly, identical reasoning applies to open-cycle, plug-flow grinding, with t replacing t, and Eq. 8 is obtained again. Considering open-cycle, fully mixed grinding, similar reasoning gives P(x) - t S(x) for surface area purposes, and

Jan 1, 1974

YEAR OF ELECTION 1922. FEDERICO GIOLITTI Torino, Italy. 1917. HERBERT HOOVER Washington, D. C. 1941. DANIEL COWAN JACKLING San Francisco, Calif. 1939. HENRY KRUMB New York, N. Y. 1942. Essington Lewis Melbourne Vic., Australia 1921. C. McDERMID London, England. 1942. PAUL DYER MERICA New York, N. Y. 1913. EZEQUIEL ORDONEZ Mexico City, Mexico. 1938. A.M. PORTEVIN Paris France 1937. JOHN V.W. REYNDERS, New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T.A. RICKARD Victoria, B.C., Canada

Jan 1, 1943

By H. R. Shidel

THIS paper summarizes the results obtained from the preliminary cementing of wells in an effort to cut off the bottom water. The object of this work was two-fold: (1) To prevent the oil sand from becoming flooded. (2) To plug off bottom water, thereby preserving the individual well and reclaiming production. Valuable suggestions and help have been given by the following named: Messrs. Kyle and La Velle, of the U. S. Bureau of Mines; Magnolia Petroleum Co.; Freed Oil and Gas Co. The cementing work was carried out under the personal supervision of L. J. Snyder. In an unpublished paper on the "Water Problem in the Augusta Field," S. K. Clark reaches the following conclusions: (1) That the great amount of water present is bottom water, occurring in the Varner sand, the main producing or the 2500-ft. horizon. (2) That the only striking connection between structure and water is in the area of the marked fault on the Ralston, E. C. Varner, and F. Varner leases in sections 8, 9, 16 and 17. (3) That the oil occurs in porous streaks, generally separated by fine-grained, well cemented sand, which is barren. Possibly two, or three such pay streaks may be found. That under a pay, fine-grained sand occurs, which is presumably barren at the time of drilling, but soon reveals water. The writer takes partial exception to the last point, because well defined shale, slate, lime, or hard sand breaks have been encountered in a great many cases, separating the pay streaks under which water is often found. This is not an invariable occurrence, as cases have been noted when the oil has been followed immediately by water in the same stratum. In an effort to overcome the water menace, the following methods of plugging were tried: (1) Plugging with wood, lead, and limit plugs. (2) Plugging with sand pumpings.

Jan 10, 1918

By J. R. Low, M. Gensamer, W. T. Lankford

THE problem of sheet metal formability is one which has received a vast amount of attention during recent years. In spite of the great amount of study and experimental work which has been devoted to this problem, many of its fundamental aspects are still not well understood. No generally satisfactory test has been developed which is capable of providing a reasonably adequate evaluation of sheet metal formability, particularly in borderline cases. Anomalies persistently arise in which a lot of supposedly satisfactory material exhibits excessive breakage when formed. This lack of suitable technological tests greatly hinders the design of new parts and the substitution of new materials in parts of existing design, frequently necessitating considerable costly trial and error experimentation on an actual production basis. When, at the beginning of World War II, it became apparent that mass production methods of forming would be required in the aircraft industry if the large numbers of military aircraft needed were to be supplied, renewed attention was focussed on the problem of sheet metal formability. It was widely recognized that the formability requirements placed on sheet metals had been steadily increasing in severity through the years, especially as greater and greater emphasis was placed on streamlined designs with the resultant freer application of doubly curved surfaces. The recent advent of several new high strength aluminum alloys of more limited formability than some of the older alloys also served to emphasize the need for new approaches to the problem. It seemed evident that progress in the technology of sheet metal forming would depend to a great extent on the development of more reliable criteria for the evaluation of formability. Although the problem is admittedly very complex, the most logical approach appeared to be through studies of the fundamental material properties of sheet metals, especially under complex stress conditions simulating those prevailing in actual forming operations. Most previous investigations have failed to make full use of existing knowledge of fundamental material properties, and in many instances have attempted correlations with properties which are now recognized as being ambiguous in nature. This investigation was undertaken, therefore, with the aim of developing methods for the study of the flow and fracture of sheet metals under combined stresses, and of making use of such methods as might be developed in

Jan 1, 1947

By J. B. Mudd

Introduction It is difficult to think of any activity on which mankind has been more dependent than mining, and certainly there is much evidence in almost every part of the world of old workings that clearly demonstrate that man from earliest times has dug and toiled to take from the earth precious stones, metals and materials that from time to time have been essential or of value to him. In step with social development and industrial and technological advances the tempo of mining activity, regulated only by the laws of supply and demand, has quickened and in this century has accelerated rapidly in keeping with its dramatic development. Indeed, the rate of change of events has been such that if it were to continue to accelerate as fast as it has over the past decade there is reason to wonder how the insatiable demands for metals and minerals are to be met in the years that lie ahead. Shallow mines containing high-grade ore deposits either have been or are being rapidly mined out and their place can only be taken in general by ore lying at greater depth, or by ore of low grade, situated for the most part in remote and in underdeveloped areas. The cost of exploration and development is rising at an alarming rate, with the result that the expenditure now required to bring a mine to production far exceeds anything previously contemplated. It is estimated that the total capital required to maintain existing operations and develop new ones during the next 5 years will be of the order of $50,000 million and of this, new capital to bring new mines to production will be of the order of $3,000 million. Today no single mining finance company can, from its own resources, find all the money for a major mining development, and as a consequence there has been a strong trend toward joint ventures and to the formation of multinational consortiums. International lending institutions already play an important part in financing many new mining projects and their participation provides the financial umbrella under which other lenders can invest with greater security. There is little doubt that to finance the costly ventures in the future, governments and international lending agencies, banks and finance

Jan 1, 1971