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By F. H. Deily, H. W. Lownie, E. A. Loria, L. W. Ledgerwood, M. W. 207-000-000-012 Mallett, J. E. Eckel

MANY investigations have been made of the residual gas content of iron and steel. Very few, if any, quantitative measurements have been made on the oxygen content of cupola-melted iron.' The fact that cast iron is a complex alloy rather than

Jan 1, 1957

Jan 1, 1940

Jan 1, 1940

By Robert G. Nisle

In conducting a pressure build-up test on an oil well, it is often necessary to shut-in the well for a short time prior to initiation of the test. The effect of such a short tern shut-in on the resulting pressure build-up curve is derived. The derivation is based on the Kelvin point-source solution and is a straight forward extension of the fundarnental theory. The magnitude of the effect is evaluatecl and illustrated by an example. It is shown that if the production subsequent to the short term shut-in is at least 10 times the duration of the shrct-in, the effect will he less than 10 per cent. INTRODUCTION It often happens that before a pressure build-up test can be made an additional valve must be mounted on the wellhead, or on arrival at the well, it might be learned that the well had been shut-in several hours the previous day because of a shortage of tankage. In such cases the question is How will such an interruption of production affect the results of a pressure buildup test This work explains how to take account of such a short term shut-in in order that the test can proceed without further delay. The solution presented here makes use of the Kelvin point-source solution used by Horne1 in his treatment of the pressure build-up in wells. Use is also made of the super-position theorem. MATHEMATICAL DERIVATION The well is assumed to have been in production at a constant rate for a relatively long time (several days or more). It is then shut-in for a short time, after which it is again placed in production at the previous constant rate. It continues to produce at this rate until shut-in for a pressure build-up test. The Kelvin point-source solution is expressed by Eq. 1. The sequence of production rates is listed in Table I. TABLE 1 — SEQUENCE OF PRODUCTION RATES Time interval Production Rate At time AT the pressure will be the resultant of the sequence of production rates shown in Table 1. An expression for the super-posed effects may be derived from this table. (Effect of + q for T + ? T) + (Effect of - q for T + ?T-t,) + (Effect of + q for T + ? T - t,) + (Effect of - q for ? T) = Resultant........(2) The desired result is obtained by substituting the effect defined by Eq. 1 for the terms in Eq. 2. The result is Eq. 3. When the logarithmic approximation is made for the exponential integrals and the terms collected the result is Eq. 4. Let T — t2 = T = flowing time following short term shut-in t2 — t1 = 6 = duration of short term shut-in Then T - t1 = r + 6 Substitution of these quantities in Eq. 4 gives p(rw ?T) = P,, -When d<<t - AT then d—&apos;-, T— approaches 1. r + AT In this case the effect of the short term shut-in may be ignored. In order to get some idea of the numerical magnitudes involved take the worst possible case, when AT = 0, that is at shut-in. If the error is made less than some maximum acceptable value at this time, it will be less than the maximum for all subsequent times. d + r Let the difference between the value of y-— and 1 be less than 0.1. Then —6+r — 1 < 0.1 S < O.l T Therefore, if the flowing time following a short term shut-in is at least 10 times the duration of the short term shut-in, the error introduced by ignoring the short term shut-in will not exceed 10 per cent of T+AT A T

Jan 1, 1957

TITANIUM is one of the most abundant elements in the minerals that make up the earth&apos;s crust but its use in industry is only a generation old; yet probably no other important commercial mineral raw material (except possibly magnesium) has undergone more changes and developments in sources of supply, in processing techniques, in uses and applications, in the past 10 years, or stands on&apos; such a threshold of still more advances. Its outstanding use today is as the oxide, and because of its extreme whiteness, high refractive index, chemical stability, and relative cheapness, it has become the white pigment used in the largest volume. New developments in the uses of titanium metal, potential and actual, may surpass the pigment use of the oxide before many years. TITANIUM-BEARING MINERALS Although a number of minerals contain titanium as the principal metal, only a few are of commercial importance. These are arizonite, ilmenite, and rutile. The other oxides, brookite, pseudobrookite, and anatase, occur in a few deposits, one at least of minor importance. The silicate titanite, and the double oxide of calcium and titanium, perovskite, occur in a few deposits in quantities sufficient to be considered as potential ores were not richer deposits of the oxides available elsewhere. Arizonite is a name given by Palmer46a to a mineral found some years ago in minute quantities in Arizona, which has the formula Fe203.3Ti02. Unexpectedly, it was found that the black titaniferous iron oxide found in large quantities on the beaches of many continental land masses corresponds in chemical composition to this formula (although ferrous oxide is always present). No one has yet been able to prove that the commercial mineral on the beaches is truly arizonite, or an allotropic modification of it, since X-ray investigations by Howard Carl and A. F. Gabriel, of the U. S. Bureau of Mines, and by the X-ray laboratory of the Chemical Department at the Experimental Station of the du Pont company, have shown only that the sand mineral gives just a jumble of lines, rather than an identifiable pattern. Lack of a better name,

Jan 1, 1949

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By C. A. Heberlein

C. A. HEBERLEIN,* New York, N. Y.-The results stated by Rey and Brevers are so startling that they are of great interest, as the concentration of a low percentage of cinnabar by differential flotation yields a high-grade concentrate in the presence of either arsenical or iron pyrite. The authors say: "Cyanide can thus be used to depress arsenopyrite and make a good cinnabar-arsenopyrite separation. A cinnabarpyrite separation could probably be effected in the same way." Corrosive sublimate at the present price of mercury would be a very expensive reagent but the expense would be justifiable if a high rate of concentration could be obtained with a high extraction. On my request, special tests were made in the Punitaqui mill in Chile along the line suggested by the authors, without any improvement of either grade or extraction. As the recovery of the cinnabar in a complex sulphide of chalcopyrite and pyrite gave unsatisfactory results, I had tests made at the testing laboratory of the American Cyanamid Co. at Stamford, Conn. As these tests turned out to be highly satisfactory, not only at Stamford but later at the mine, they are presented here. [AMERICAN CYANAMID TEST FEED PER CENT Si02 66.54 A12032.08 CaO0.70 MgO 0.00 Alkalis1.78 Fe15.63 Cu0.44 S9.42 Hg0.45 OZ. PER TON Ag0.95 Au0.151 Screen Analysis of Tailings, Per Cent Plus650.0 Plus 1001.32 Plus 15020.75 Plus 20019.85 Minus 20058.08] The pulp had a density of 22 and a pH of 7.8. Total time of conditioning was one minute. The reagent added was Texas fuel oil, 0.116lb. Of 33.7 Bé. gravity containing 0.9 per cent sulphur. Frother, 0.062 lb. of No. 5 pine oil. Rate of concentration of mercury was 25.7: 1 [ ]

Jan 1, 1941

By Arthur H. Redfield

In estimating the unmined petroleum reserves of Central America, it is not feasible to employ the methods that have been worked out in thc oil fields of the United States. No producing wells have been brought in and no drilling sections have been made public. It is accordingly necessary to fall back on a crude "barrels per square mile" estimate. The method chosen is a comparison of the structure of the foreign field of unknown reserves with that of some supposedly analogous North American field of which the reserves have been estimated. This method makes no pretense at scientific accuracy, but furnishes a working basis for an estimate. The areal geology of Central America is illustrated in the inap prepared by Sapper and more recently in the geologic map of North America accompanying U. S. Geological Survey Professional Paper No. 71, "Index to the stratigraphy of North America." Disregarding for the present the narrow Quaternary coastal plains and alluvial deposits of the river valleys, three chief zones may be distinguished. These arc: A zone of late eruptive and effusive rocks; a zone of highly folded prr-Cambrian(?) or early Paleozoic crystalline schists and slates, considerably intruded by pre-Tertiary plutonic rocks; and a zone of more or less folded sediments, chiefly of Cretaceous or Tertiary age. The zone of late eruptive and effusive rocks of Central America begins in southeastern Chiapas, Mexico, and extends, with increasing breadth, across southern Guatemala, across practically the whole of El Salvador, and across southern Honduras to the valley of Rio Goascorhn, where the igneous zone attains a width of about 100 mi. (160 km.) East of the Goascordn Valley late eruptives and effusives play a subordinate part, being confined largely to thc Departments of Valle and Choluteca. Dikes and sills of igneous rocks intrude the sedimentary formations of central and northern Honduras. Late igneous rocks cover about four-fifths of the area of Nicaragua. In Costa Rica, late igneous rocks form the diagonal ranges of the Sierra de Guanacaste and the Cordillma Central, and play a part in the upbnild-

Jan 1, 1923

By Arthur H. Redfield

In estimating the unmined petroleum reserves of Central America, it is not feasible to employ the methods that have been worked out in thc oil fields of the United States. No producing wells have been brought in and no drilling sections have been made public. It is accordingly necessary to fall back on a crude "barrels per square mile" estimate. The method chosen is a comparison of the structure of the foreign field of unknown reserves with that of some supposedly analogous North American field of which the reserves have been estimated. This method makes no pretense at scientific accuracy, but furnishes a working basis for an estimate. The areal geology of Central America is illustrated in the inap prepared by Sapper and more recently in the geologic map of North America accompanying U. S. Geological Survey Professional Paper No. 71, "Index to the stratigraphy of North America." Disregarding for the present the narrow Quaternary coastal plains and alluvial deposits of the river valleys, three chief zones may be distinguished. These arc: A zone of late eruptive and effusive rocks; a zone of highly folded prr-Cambrian(?) or early Paleozoic crystalline schists and slates, considerably intruded by pre-Tertiary plutonic rocks; and a zone of more or less folded sediments, chiefly of Cretaceous or Tertiary age. The zone of late eruptive and effusive rocks of Central America begins in southeastern Chiapas, Mexico, and extends, with increasing breadth, across southern Guatemala, across practically the whole of El Salvador, and across southern Honduras to the valley of Rio Goascorhn, where the igneous zone attains a width of about 100 mi. (160 km.) East of the Goascordn Valley late eruptives and effusives play a subordinate part, being confined largely to thc Departments of Valle and Choluteca. Dikes and sills of igneous rocks intrude the sedimentary formations of central and northern Honduras. Late igneous rocks cover about four-fifths of the area of Nicaragua. In Costa Rica, late igneous rocks form the diagonal ranges of the Sierra de Guanacaste and the Cordillma Central, and play a part in the upbnild-

Jan 1, 1923

By James W. Dally, William L. Fourney, Anders Ladegaard Peterson

For the past 3 years, the authors have been conducting research sponsored by the National Science Foundation (RANN) to improve the process of excavation by drilling and blasting. The approach followed has been experimental where the development of stress waves and fractures initiated at the bore hole have been investigated in order to obtain a complete understanding of the dynamic fracture process. The second step in the approach has been to introduce modifications in the drill and blast procedure which will permit closer control of the fracture process. The laboratory investigations involve high speed photography where the dynamic fracture process is recorded with a Cranz-Schardin 1, 2 multiple-spark camera. The camera is equipped with 16 spark gaps which are pulsed at 25 K volts to produce an intense but very short (0.5 sec) flash of light. The camera is capable of recording 16 photographs of a dynamic event at framing rates which can be varied from 30,000 to 1,500,000 frames per second. The exposure time is sufficiently short to stop motion associated with detonating explosive charges and to make visible the details of the fracture process at a bore hose. The bore hole in a massive intact rock formation is modelled with a two dimensional plate containing a circular hole to represent the bore hole. The model material employed is a transparent polyester known commercially as Homalite 100.* This polymeric material is extremely brittle as evidenced by its extremely low fracture toughness of [ ]. The fracture toughness is a measure of the ability of a material to resist the propagation of flaws or small cracks. In comparison, Schmidt3 has recently measured the fracture toughness of Salem limestone and determined [ ]. Thus, the Homalite 100 should closely model the brittle nature of rock where fractures occur at small flaws and propagate without any apparent plastic deformation. Homalite 100 is also birefringent, which indicates that it becomes optically anisotropic when subjected to either static or dynamic loads. Circularly polarized light is transmitted through the loaded Homalite 100 model in a polariscope4 and the birefringence produces an optical interference pattern which is called a fringe pattern. For dynamic photoelasticity, the multiple-spark camera is equipped with polaroid filters to produce the circularly polarized light required to generate the photoelastic fringe patterns. An example of a singlespark frame showing a fringe pattern from a typical experiment is presented in [Fig. 1]. The photograph was taken 0.000072 sec (72 sec) after the detonation of the explosive charge. The circular fringes are due to the outgoing dilatational or P type stress wave and travel with a velocity of 85,000 in. per sec (2260 m/sec) in the Homalite 100. The P wave is followed by a second lower velocity stress wave known as the shear or S type wave which propagates at a velocity of 49,000 in. per sec (1245 m/sec). In the local neighborhood of the bore hole, several radial cracks are visible. These cracks propagate at essentially a constant velocity of 15,000 in. per sec (380 m/sec) prior to arrest. The fringes about the crack tips and in the local region of the bore hole are primarily due to the residual gases contained in the bore hole after the explosive charge was detonated. Sixteen frames similar to this one are recorded during the experiment to give full field visualization of the dynamic event at 16 discrete times over its duration. The fringe order number N is related to the difference in the principal stresses of and 02 according to a stress optic law4: [ ] where f0 = material fringe value, and h = model thickness. The wholefield dynamic-fringe patterns provide a basis for simultaneously observing the interaction between propagating cracks and the stresses which drive these cracks. Fracture Control Experiments Improvements in the efficiency of the drill and blast procedures must involve close control of the fracture process following the detonation of an explosive charge in a bore hole. By control it is implied that the number of cracks initiated and the location of each crack on the wall of the bore hole can be specified. Control also, involves orienting each crack and maintaining the crack path and velocity until the specified crack length is achieved. If the entire fracture process can be controlled, then rounds can be designed to optimize volume removed. fragment size and minimize costs. One area of blasting where fracture control is vitally important is in underground excavation where the strength and stability of the rock walls must be maintained and smoothness and precision of the walls must be achieved. The smooth blasting method is one of the most commonly employed procedures for achieving some degree of fracture control. In smooth blasting, the central region of material is first removed, and then the final row of closely spaced undercharged or cushioned holes are fired to remove the final volume and produce a smooth wall. In some instances, unloaded or dummy holes between the loaded holes are recommended to guide the fracture plane. This investigation pertained to an evaluation of 3 features of the smooth blasting process. These included (a) the effect of stress reinforcement on fracture by simultaneously firing 2 charges; (b) the influence of a dummy hole on control of the fracture planes between 2 simultaneously fired charge holes; and (c) the influence of dummy hole spacing on fracture plane control.

Jan 1, 1979

By D. W. Smith

THE beta solid solution phases of the systems copper-zinc, copper-aluminum, copper-tin and silver-zinc are structurally analogous.1 R. F. Mehl and 0. T. Marzke2 have shown that the a phase upon segregating from the 0 phase in the system copper-zinc takes the form of needles lying parallel to a [111.] direction or some similar direction, such as [556], of the parent solid solution, and that the a phase upon segregating from the ß phase in the system copper-aluminum also takes the form of needles. By analogy they assume that in this case also the segregate needles lie parallel to the [111] or [556] direction in the ß lattice. The purpose of this investigation is to determine whether the structures resulting from segregation of the a phases from the respective 0 phases of the systems copper-tin and silver-zinc are analogous to those obtained by Mehl and Marzke in the systems copper-zinc and copper-aluminum.

Jan 1, 1932

By Joseph M. Dawson

Although there was a very great increase in drilling activity along the fault line of south Texas during 1937 as compared with the previous three or four years, and although seven new fields were discovered, it cannot be said that any major development of importance took place. There were slightly over 550 completions during 1937, of which nearly 350 were oil wells as compared with some 275 the preceding year, of which 169 were oil wells. This increase in drilling activity was occasioned almost entirely by the greater interest in and development of Austin chalk production, principally in Caldwell, Guadalupe and Bastrop Counties. Seven fields were found, of which a brief description is given in Table 3. None has as yet assumed anything of major importance, and it is doubtful whether any will be classified as major discoveries through further development. Two were producing from the Edwards limestone, one from serpentine and the other four from the Austin chalk; the latter may be classified as extremely erratic in nature. The major discouraging feature of the year was the rise and subsequent fall of interest and importance of Austin chalk production. Many new operators came into this district to drill and produce Austin chalk oil toward the first of the year, but in the latter months the production decline from this formation was so rapid and the production so erratic that drilling operations fell off materially and interest largely abated. This was particularly true of the Branyon field in Caldwell County, and the same statement is applicable to the Pearsall field, Frio County. The latter field, covering some 5000 acres and owned and controlled entirely by the Amerada and Rycade, had early completions from the Austin chalk as high as 22,000 bbl. per day. The decline was extremely rapid and the maintained production from 17 wells is only around 700 bbl. per day after a total recovery of less than one-half million barrels. Present estimates of recoverable oil from Chalk vary from 2000 to 5000 bbl. per acre. A new process for the completion of producing wells from the Edwards limestone, particularly applicable to old producing areas, was developed, in that the penetration of the Edwards lime in drilled wells is now only 1 or 2 ft. as compared to between 15 and 75 ft. in wells drilled several years ago. Many new wells have been drilled in old Edwards lime producing

Jan 1, 1938

By V. R. Garfias

EVEN before the arrival of Cortes in 1519, the history of Mexico was closely linked to that of its mineral production; the mining activities of the Aztecs being thus described by Clavigero, one of the early historians: In the mountains of Anahuac there abound in veins all kinds of metals, and infinite variety of other fossiliferous products. The Aztecs obtained gold from the countries of the Cohuijques, of the Mixtecas, of the Zapotecas and from various other places. They gathered that precious metal usually in grain, from the sands of the rivers, keeping a certain portion for the crown. They obtained silver from the mines of Taxco, of Tzumpango and others; however, this metal was not as esteemed by them as by other neighboring nations. They had two kinds of copper; one hard, which they used instead of iron to make sickles, lances and all kinds of rural and military instruments and another, soft, with which they made kettles, goblets and other receptacles. This metal abounds mainly in the province of Zacatula and in that of Cohuijques, which at present is in the kingdom of Michoacan. They obtained tin from the mines of Taxco and lead from those of Izmiquilpan, located in the country of the Otomiea. From the tin they made money, and the lead, we know they sold in the market places, but we ignore the uses to which they applied it. They also had mines of iron in Tlaxcala, in Taxco and in other places; but they either had not discovered them, or did not know how to make use of the metal they contained. In Chilapa there were mines of mercury, and in other places there were mines of sulphur, alum, vitriol, cinnabar, cohre and of a white earth which they esteemed highly. As regards mercury and vitriol, we do not know of what use they were to them; the other metals they used in paintings and dyes. There were then great abundance of amber and asphalt-bitu- men of Judea--on the coast of the seas and many cities of that territory paid tribute of one and the other to the kingdom of Mexico. They mounted the amber in gold, and it was only used as ornament and display by them. With the asphalt they made certain perfumes. The following extracts dealing with pre-Colonial gold are taken from the famous "Cartas de Relación" to Charles V, in which Cortea described the progress of the Conquest: . . . here there came two chiefs who owned lands in the valley; one four leagues down the valley and the other two leagues up the valley and they gave me some gold necklaces of little value and seven or eight girls. . . . . . . that day I left the City of Churultecal and traveled four leagues to some villages of the City of Cuasucingo where the natives received me very well and gave me women and pieces of gold. . . .

Jan 1, 1937

By C. A. Wright

The average lead and zinc content of the ores mined and milled in the Joplin district is low as compared with that of other lead and zinc deposits throughout the United States. Because of this fact and of the high grade of the concentrates, the ratio of concentration is unusually high. Most of the operating companies have aimed to produce as high a grade of concentrate as possible in order to obtain the highest price for their product. They have done this at the sacrifice of the percentage of zinc recovered. The average percentage of zinc recovery is from 60 to 70 per cent. For percentage of recoveries from actual mill tests, see tables. The concentration is commonly effected by crushing the ore to ½-in. (12.7 mm.) size and subjecting it to a roughing and cleaning over two or more large Cooley jigs, of the Harz type, the finer sands being treated on the usual types of sand and slime tables. The treatment of slimes by flotation is being tested at several of the larger mills. Coarse Concentration When the ore has been hoisted from the mine it is dumped onto a chute leading to a grizzly made of iron bars, usually heavy rails, spaced 4 to 5 in. (101 to 127 mm.) apart. The oversize is caught on the grizzly, the mineralized pieces are broken with sledge hammers so as to pass through, and the boulders that are practically barren are sorted out by hand and trammed to the waste-rock pile. The proportion of waste rock thus sorted out varies from a fraction of 1 per cent. to 15 per cent., depending on the nature of the rock. Crushing The undersize material, 5 in. (127 mm.) or less in diameter, passes through the openings of the grizzly into the mill hopper below. From

Jan 1, 1918

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3&apos; phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou&apos; zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß&apos; was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß&apos; phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13&apos; was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß&apos; which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß&apos; on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß&apos; phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß&apos; and to structures, and the 4, structure can be derived from the 0&apos; structure by a small movement of atoms mainly in the direction of the cube diagonal.4&apos;5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p&apos; structure and transformation from ß&apos; to requires a large fraction of the atoms to change position. It has been shown that the ß&apos; transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By C. L. Thornburg

FLANKING the Valley of Mexico on the northeast is a mountain range known as the Sierra de Pachuca. This northwesterly-trending range is about 30 miles long and 5 miles wide, its summit attaining an elevation of more than 10,000 feet above sea level, or 2000 feet above the valley floor. Pachuca, a town of 50,000 inhabitants, lies nestled at the southwest base of the range, 60 miles northeast of Mexico City. Three miles to the east, just over the summit and on the northeasterly slope, is the mountain town of Real del Monte with a population of about 20,000. These are the two principal towns in a 40-sq mile area whose yield has brought the district to its high rank among the world&apos;s silver producers. Total production probably exceeds 1.25 billion ounces of silver and 4.5 million ounces of gold. Exploitation by the Spanish was under way by 1530. As the mines were deepened operations became handicapped by the inadequate method of handling water with horse whims and bull skins. To offset this disadvantage a two-mile drainage tunnel was started in 1749 and completed ten years later. John Taylor of London acquired the mines from the third Count of Regla in 1824 and formed the Compania de Real del Monte y Pachuca. Two years later Cornish pumps were brought from England. A Mexican company purchased the British interest in 1848 and within a few years resumed an old project of driving a second, lower three-mile drainage tunnel, completing it in 1857. After American interests acquired control of the property in 1906 operations expanded to an unprecedented scale, despite periods of political strife, unstable prices, labor problems, and a growing burden of taxation. An idea of the scale of operations may be gained from records of the last two decades prior to 1947, the last year for which production information is at hand, during which time production ranged from 1.4 million to 1.1 million tons per year, and the combined development and exploration, exclusive of diamond drilling, amounted to about 18 miles annually. Pachuca differs from Zacatecas and some other Mexican silver vein districts that flourished and declined in earlier centuries in that a substantial part of its total production was made after 1900. While the district&apos;s accelerated activity in this century was largely due to the successful application of the cyanide process to the treatment of the ores, improved pumping methods, and new mechanical equipment, it was at the same time stimulated by the opening up of important new orebodies as a result of active and extensive exploration of the vein system. Some of these orebodies were found on veins which terminate upward far below the surface, and though these particular veins do not crop out, they show relationship with a type of alteration which may be their surface expression. The district has been studied by many able geologists, and a large store of information has been accumulated, much of which is recorded in published as well as private papers. Wall Rocks Extrusive Rocks: The Sierra de Pachuca is a thick accumulation of Tertiary eruptive rocks consisting mainly of flows, breccias, and tuffs. Numerous recognizable volcanic vents within the range itself manifest that the range was built up by material ejected from these vents. The maximum thickness of the volcanic pile is not known, but from deep exploration and from relationship with Mesozoic sediments to the north and east it is inferred that the average thickness in the main part of the district may be at least 6000 ft. The extrusive rocks comprise four general types, which in ascending order of age are: andesite, rhyolite, dacite, and basalt. The veins are confined largely to the andesite, the dominant rock of the region. Characteristically this rock is augite andesite, but it includes comparatively acidic as well as basic layers, the acidic strata being

Jan 1, 1952

By Mark Malamphy

DURING colonial times, Brazil was famous for the richness of her alluvial gold deposits. Paul Ferrand has estimated that the gold produced during the period from 1700 to 1820 was the equivalent of some 64 million pounds sterling. Since that time, most of the more prolific alluvial deposits have been exhausted. A few gold mines are still func-tioning, notably the Morro Velho mine, which is one of the deepest mines in the world. Today, the gold production of Brazil is insignificant when compared with world figures, but there are still many gold-bearing regions and it is probable that in at least some of them profitable returns would result from an exploitation program taking advantage of all the most modern innovations in gold mining and ore treatment on a large scale. In order to demonstrate the value of some of these abandoned pros-pects and stir up interest in increasing the national gold production, the government has stimulated research. Experimental plants have been and are being established in various places, and tests on large quantities of ores are being carried out on a semicommercial basis. The Geological Survey of the State of Minas Geraes is very active in this line and the Federal Institution is also showing an increased interest in the matter. One of the lesser known gold-bearing regions of Brazil is in the vicinity of Lavras, in the State of Rio Grande do Sul. Gold was first reported from this region in the early part of the nineteenth century. In 1811, D. João VI sent an experienced prospector from Minas Geraes to investi-gate the validity of the reports. According to the reports of Baron

Jan 1, 1934

By Walter J. Johnson

The coals in northern Wyoming and Montana are free-burning and non-caking and range from lignite to bituminous C in rank. Strip and underground mining are employed to supply railroad, utility, industrial, and domestic fuel. The market area includes Iowa, Nebraska, Minnesota, North and South Dakotas, Wyoming, Montana, the Pacific Northwest, and western Canada. THE larger producing coal mines in northern Wyoming are located in the Powder River Basin lying between the Black Hills region of South Dakota, eastern Wyoming, and the Big Horn Mountains in north central Wyoming, see Fig. 1. The mines are located particularly in the area along the route of the Chicago, Burlington & Quincy Railroad from Gillette, Wyo., to a point approximately 15 miles northeast of Sheridan, Wyo. Fig. 2 is a graph of coal production in the state of Wyoming from 1918 to 1951. Across the Big Horn Mountains lies the Big Horn Basin, situated between the Big Horn Mountains and the Rocky Mountains proper. Mining in the Big Horn Basin is almost entirely confined to a small area known as the Gebo Field, near the town of Kirby, which is located on the Chicago, Burlington & Quincy Railroad. This paper will describe present operating areas, making only brief reference to the history of mining and marketing primarily because of the large area to be discussed. The coal beds presently mined in the Powder River Basin are all of Tertiary age and are of Fort Union and Wasatch formations of Paleocene and Eocene ages, see Fig. 3. The Fort Union formation, consisting of 2000 to 3200 ft of alternate sandstone, shale, and coal, is divided from oldest to youngest into the Tullock, Lebo Shale, and Tongue River members. Most of the mineable coal is in the Tongue River member, which is 500 to 800 ft thick. The Carney coal bed, varying from 7 to 20 ft in thickness, is considered the base of the Tongue River member. About 85 ft above the Carney is the Monarch bed, ranging from 18 to 42 ft in thickness. At approximately 210 ft above the Monarch is what is locally known in the Sheridan district as Dietz No. 3 bed, which varies from 12 to 30 ft in thickness. One hundred feet above the Dietz No. 3 is Dietz No. 2 bed, which is 7 to 12 ft thick. At about 100 ft above the Dietz No. 2 is Dietz No. 1 bed, 7 to 15 feet in thickness. Two hundred and fifteen feet above Dietz No. 1 is the Smith bed, approximately 5 ft thick. One hundred twenty-five feet above the Smith is the Roland bed, which is estimated to be approximately 13 ft thick. The Roland bed is considered the base of the Wasatch formation, which in the Powder River Basin is 1000 to 3500 ft thick and is composed largely of shale, sandstone, and coal. The foregoing measures are the only ones above the Tongue River member that have been mined in the Sheridan field. To the east of the Sheridan field, particularly in the area of Gillette, the Roland bed is considerably thicker and is considered the thickest and most extensive coal bed in Wyoming, reaching a maximum thickness of 106 ft. From 125 to 225 ft above the Roland lies the Arvada bed, average thickness 9 ft. Three hundred seventy-five to four hundred feet above the Arvada is the Felix bed, which reaches its maximum thickness of 30 ft near Echeta on the Chicago, Burlington & Quincy Railroad. East of the Powder River the bed averages more than 10 ft in thickness, but it thins in a northwesterly direction. The highest mineable coal in the Powder River field is the Healy bed, about 400 ft above the Felix bed and exposed only in the highest parts of the area where much of it has been burned along the outcrop. Where it has not been burned, the thickness at most of the outcrops is 10 to 15 ft.

Jan 1, 1954