Search Documents

By J. M. Blank, V. A. Russell

When the nucleation of silicon on a sapphire substrate is accomplished by gradually decreasing the substrate temperature while subjecting it to a constant impingement rate of hydrogen and silicon tetrachloride, the resulting deposit is characterized by widely separated islands of silicon scattered over an "open sea" of sapphire. Analysis shows that nucleation takes place mainly on sites of large adsorption energy, about 85 kcal per mole, and small surface concentration, about 108 cm-2. Crystal growth proceeds rapidly on these nuclei and results in enough depletion of Sicl4 from the ambient gas to suppress further nucleation. The technological importance of single-crystal films on dielectric substrates has prompted considerable work on the deposition of silicon on sapphire. This paper is concerned with the deposition of silicon, by the reduction of silicon tetrachloride with hydrogen, onto heated sapphire substrates. The apparatus consisted of a temperature-controlled container for the silicon tetrachloride along with gas lines and flow meters necessary to convey a hydrogen-silicon tetrachloride mixture to a reaction chamber constructed of quartz tubing. Heat for the substrate was provided by means of an inductively heated graphite susceptor. The observations pertinent to the present discussion were made with an American Optical Co. high-temperature microscope which allowed us to make motion pictures of the deposition process at a magnification of approximately 50 times. Two main categories of experiments were carried out: one on determination of critical condensation temperatures and the other on the deposition of epitaxial silicon films on the sapphire substrates. Critical condensation temperatures were determined in the traditional way by raising the substrate temperature well above that at which condensation could be expected at the impingement rates being studied and then gradually lowering the temperature until the condensation of the first silicon was observed. This was done initially with ellipsometry-type detection but it was soon discovered that the deposits were occurring as widely separated islands and groups of islands scattered over an "open sea" of sapphire. We have called these archipelago formations. They were most easily detected by optical microscopy. Data gathered from experiments of this type have been collected in Table I. Motion pictures of the formation of archipelago patterns show that the nucleation period lasts about 10 sec if the substrate temperature and impingement rate are kept constant. Essentially all of the nuclei are formed in a few seconds and all subsequent silicon deposition merely adds to the size of the established nuclei. After an archipelago formation has matured at a given substrate temperature and impingement rate, it is very difficult to stimulate any further nucleation in the open space between islands. Lowering the substrate temperature will occasionally stimulate nucleation but increasing the impingement rate hardly ever produces any more new nuclei. It should also be emphasized that the nucleation rates appear to be very small, about 104 cm-2 sec-1. They will receive special attention in the analysis section. Another series of experiments was performed employing a systematic variation of substrate temperatures and impingement rates approximating those expected to produce epitaxy. Sapphire substrates with surfaces normal to the 2233 direction were used. In contrast to the procedure that produces archipelago patterns, these films were deposited by raising the substrate temperature to a desired value at which time the silicon tetrachloride and hydrogen flow was begun. Of course, these depositions produced mainly films that were continuous. After removal from the deposition chamber, the substrate and silicon film were examined microscopically to determine the nature of the deposit and by X-ray diffraction to determine the extent to which a single-crystal film had been achieved. Results of these experiments are summarized in Table 11. Of interest for the present analysis is the fact that epitaxy appears to be confined to a fairly narrow temperature range between about 1050" and 1150°C. This also will be discussed in the analysis section. ANALYSIS In this section we shall apply nucleation theory to the data presented above with the objective of testing

Jan 1, 1967

By G. W. Tracy, R. D. Carter

Numerical calculations were made to determine the behavior of reservoirs with high-pressure drawdown and wide well spacing where the initial productivity is low and the wells are completed by hydraulic fracturing. The two-phase flow equations were solved for the flow into a single well. This well was assumed to be producing from a reservoir with hydraulically created horizontal fractures (four different systems with fractures were studied). For comparison purposes, additional two-phase flow calculations were made assuming a reservoir with uniform rock properties. The two-phase flow results were also compared with the conventional calculation methods, which do not include the effect of saturation gradients resulting from a simultaneous flow of oil and gas which are normal to this type reservoir. It was found that the conventional methods predict (1) a high and too optimistic value of ultimate recovery, (2) a high producing rate and a high reservoir pressure at a given oil recovery and (3) a low trend of gas-oil ratio with oil recovery. Included in the two-phase flow calculations were provisions to control the oil production rate by an allowable rate and, also, by a gas-oil ratio penalty rule. For the systems with hydraulic fractures, the producing rate was controlled by the gas-oil ratio penalty rule for most of the life. This is in contrast to the system with uniform rock properties which went "on decline" almost immediately. An unexpected characteristic of the systems which included fractures was the early rise in producing gas-oil ratio from 730 cu ft/bbl to approximately 1,200 cu ft/bbl, followed by a "leveling off" before the normally expected gas-oil ratio rise began. Additional features which are a result of hydraulic fracturing are (I) greater ultimate recovery, (2) higher average producing rates and (3) a lower average reservoir pressure at a given oil recovery. INTRODUCTION Some oil fields discovered during the past few years are producing from certain volumetric ally controlled reservoirs (often referred to as solution or internal gas- drive reservoirs) which are characterized by high-pressure drawdown at the wells. Since the available pressure drawdown at a well is limited by the static reservoir pressure and the producing rate is controlled by the available drawdown, wells completed in this type of reservoir usually produce at a rate less than the allowable from the time of completion. Because of this, this type of reservoir is referred to as a low productivity reservoir. Economic considerations require the use of wide well spacing and well stimulation by hydraulic fracturing to make commercial wells in this type of reservoir. Performance predictions for volumetrically controlled reservoirs have been made using a combination of two standard equations. 1. The "Schilthuis" or "Muskat" type material balance equation is used to relate the average reservoir pressure and the cumulative oil recovery. 2. The results from the material balance equation and the productivity factor as described by Pirson' are used to relate the cumulative recovery with producing rate and time. The material balance equation assumed uniform pressure and liquid saturation conditions throughout a reservoir. The steady-state radial flow formula allows for a pressure gradient toward a well but assumes uniform liquid saturation. These calculation methods are adequate for application to reservoirs wherein the drawdown at the well to realize satisfactory producing rates is small compared to the total pressure. In low productivity, volumetrically controlled reservoirs, the pressure drawdown at the well is large cornpared to the total pressure. Although a precise number cannot be given for the magnitude of a large pressure drawdown, values in excess of 1,000 psi would definitely be included. For practical considerations, this usually occurs when the formation flow capacity is less than about 100 md-ft. However, this limit of formation flow capacity will vary with the well producing rate. The low pressure in the neighborhood of the well which results from a high drawdown causes evolution of large volumes of gas. This causes the gas saturation to be higher near the well than at a greater distance—-hence, a non-uniform gas saturation. Also, the relationship between the relative permeability to oil (K/K) and gas saturation is nonlinear but decreases approximately in an exponential way with increases in gas saturation. Because of this, the following chain reaction is established.

By P. H. Wendland

Calculations are presented for the design of a silicon photodiode in which the incident light beam makes multiple passes between the detector surfaces. Total internal reflection is used for this "light-trapping" effect. By this means, the optical path length can be extended to several millimeters, while the electrode separation remains less than 102 cm, as required for nanosecond response time. Data are presented for a Schottky barrier photodiode constructed on a multiply reflecting silicon base wafer. It is shown that the long-wavelength response is considerably extended in such structures without a corresponding sacrifice in high-speed response. The development of efficient and powerful lasers at 1.06 p has stimulated interest in detectors which operate at this wavelength. In typical silicon photodiodes, for detecting 1.06 p radiation, the requirements for high speed and high sensitivity are mutually exclusive. Since the absorption coefficient is only 25 cm-', a lo-'-cm path length is required to absorb 92 pct of the incident 1.06 p radiation. If the electrode separation is greater than 10 cm, however, the carrier transit time will be greater than 1 nsec. This problem can be solved by allowing the incident light beam to make multiple passes between the electrodes. The optical path length can then be extended to several millimeters, as required for complete absorption, while the electrode separation remains less than 10' cm, as required for nanosecond response time. In a typical photodiode geometry, one ohmic contact and one rectifying contact are formed on the two opposite surfaces of a base wafer, and the wafer thickness determines the electrode separation. The objective of the multiple reflection design is to allow all 1.06 p radiation to enter the detector front surface and to form the back detector surface so that no 1.06 radiation can exit. Total internal reflection at the back detector surface is well-suited for light trapping of 1.06 p radiation because the relatively large dielectric constant of silicon leads to a critical angle of 16.5 deg for total internal reflection. LIGHT TRAPPING It is well-known that, as light passes from one medium such as air into another medium such as glass or silicon, the angle of refraction is always less than the angle of incidence. In the limiting case, where the incident rays approach an angle of 90 deg with the normal, the refracted rays approach a fixed angle +, beyond which no refraction is possible: this is called the critical angle. It follows from Snell's law that where = critical angle, n - index of refraction of air, n' - index of refraction of the medium. Applying the principle of reversibility of light rays, all internal angles of incidence greater than +, will produce total internal reflection and "light trapping". The index of refraction of silicon at 1.06 p is 3.5,' and the critical angle is thus 16.5 deg. Fig. 1 shows these relationships for silicon. This very small critical angle in silicon is significant because all incident angles between 16.5 and 90 deg will produce total internal reflection and "light trapping". This effect can be implemented with a "prismlike" geometry, so that incident light can be introduced into the sample without loss and "trapped". PHOTOSIGNALS A precise knowledge of the absorption coefficient at 1.06 in silicon is of critical importance to the design of fast and efficient silicon photodiodes for 1.06 radiation. Dash and newman2 show a value of 25 cm-l, and our measurements have corroborated this value. Assuming that the collection of photoinduced minority carriers is perfect, the quantum efficiency of a photodiode is dependent only on the absorption coefficient. It then follows from Lambert's law that where QE is the quantum efficiency in pct, a is the absorption coefficient, d is the optical path length, and the reflectivity at the surface is assumed to be completely suppressed by an optical interference layer. Fig. 2 gives the maximum quantum efficiency for 1.06p radiation of a silicon photodiode with optical path length d, using Eq. [2]. The ultimate response time of a fully depleted photodiode to an incident light pulse can be considered to be the arrival times of all photoinduced carriers at the contacts, i.e., the minority carriers at the junction interface and the majority carriers at the oppo-

Jan 1, 1968

The accompanying sketch shows the interesting position of Salt Lake City with reference to Western mining areas and justifies its title "The Center of Western Mining." In the last twenty years, the area embraced within a circle of 600 miles radius with Salt Lake City as its center has produced 79.87% of the gold, 91.9% of the Silver, 77.47% of the copper, 53.61% of the lead and 26.55% of the zinc produced in the United States, including Alaska. This area also contains the greatest coal deposits of the continent, some of the greatest oil deposits, great iron deposits and many other important mineral resources. The 600-mile circle contained 69% of the active operators of other than coal mines and 40% of the men employed in mines other than coal mines of the United States, including Alaska, for the four-year period ended with 1923.

Jan 1, 1925

By Paul A. Hodges

With plant start-up slated for early 1966, Palabora Mining Co. will take its place among the large copper mining properties of the World. Located near the town of Phalaborwa in the Lowveld area of Transvaal Province, approximately 250 air miles northeast of Johannesburg, Palabora is the result of a cooperative project between Rio Tinto-Zinc Corp. and Newmont Mining Co. Other large shareholders are American Metal Climax, Inc., Union Corp. Ltd., and Selection Trust Ltd. Earliest known mining activity in the area is thought to date back about 400 years, when the Bantu tribes were migrating southward from the great lakes of Central Africa. Old workings and hand tools have been found in numerous places on the flanks of Loolekop, the hill that contains the outcrop of the Palabora orebody. Nearby ruins of small furnaces give added evidence of the knowledge of copper smelting possessed by these natives.

Jan 3, 1966

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually aver- age about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment.

Jan 9, 1953

Year of Election 1959 Andrew Fletcher, New York, N Y "For his outstanding leadership in the lead and zinc mining industries, and for his able and devoted services to the Institute as its Treasurer and President, and as a Director for many years " 1917 Herbert Hoover, New York, N Y 1955 George M Humphrey, Cleveland, Ohio 1950 Zay Jeffries, Ptttsfield, Mass 1942 Essington Lewis, Melbourne, Vic, Australia 1959 John M Lovejoy, New York, N Y "For his distinguished service to the Institute, for his outstanding contributions in furthering the professional status of petroleum engineers, for his pioneering in application of engineering to petroleum production, and for his outstanding record of public service on behalf of the petroleum industry " 1957 Donald H McLaughlin, San Francisco, California 1957 C H Mathewson, New Haven, Connecticut 1938 Albert M Portevin, Parts, France 1957 Fred Searls, Jr, New York, N Y

Jan 1, 1960

MISSOURI SCHOOL OF MINES The Missouri Mining Association has enjoyed a very good year. Last October the society was reorganized and the following officers elected for the year: E. Ross HOUSHOLDER, President, ORE N. MANESS, Vice-president, WILLIAM REBER. Secretary, RUAL CHAVEZ, Treasurer. The head of our mining department, Prof. C. E. Forbes, is now serving as a Major in the United States. Army. We were fortunate in having. Prof. Chas. E. Locke, of Boston, with us for part of the winter to take charge of the senior mining work. During the autumn and winter months we had a number of informal smoker lectures in Norwood Hall. Among the speakers at these meetings were: H. A. Buehler, Missouri State Geologist; Chas. E. Locke, Boston, Mass.; V. H. Hughes, Tulsa, Okla.; Dorsey Lyon, Washington; D. C.; Prof. G. H. Cox, Professor of Geology, Rolla, Mo.; together with a number of returned alumni.

Jan 8, 1918

By P. Barnes

SEVERAL interesting and important considerations may be based upon an analysis of the cost of producing Bessemer rails, and the facts thus set forth may be much more clearly emphasized by reducing each item of cost to its own fractional proportion of the sum total in each branch of the manufacture. The estimate given below is not absolutely complete in minuteness of detail, but it may be fairly taken as a basis for the suggestions to be noted : Perhaps the most striking comments that can be made upon this statement are those arising from a consideration of some of the smaller items, and even the least of these quite loses its insignifi¬cance when its proportion of the whole is expressed in actual money, as for the work of a year, or even for a single day. Thus, if the item A 5 be considered, the importance can be clearly

Jan 1, 1877

A SERIES of awards for men and women in indus-try who by their inventions, heroisms, vision, and powers of mediation are contributing daily to the life and well-being of America in a substantial way, will be given by the Harmon Foundation. The series, to be known as "Awards to Honor Men in Industry," consists of two cash prizes, $1,000 and $500 each, accompanied by a gold and silver medal respectively, and 100 bronze medals. No one above the rank of foreman will be eligible. Because of the diversity of .American indus-try, the Foundation is planning to confine its awards during the first year to the following branches of man-ufacturing: automotive, building, electrical, metal and textiles, including clothing. The Harmon Foundation invites the general public, newspapers, organizations and employees to bring to its attention such persons as they may deem worthy of the award.

Jan 3, 1928

By D. Moskowitz

IN the course of a general investigation of boride systems, sponsored by the Office of Naval Research, various vanadium boride powders of relatively good purity were prepared which could be used for a determination of the phases present. The X-ray pattern of one of these lots showed, in addition to the known VB1 and VB22 phases, an additional phase, almost certainly of composition V3B4, isomorphous with Cr3B4, Cb3B4, Ta3B4, and Mn3B,. Its pattern fitted in well with the indices worked out by Kiessling for Mr3B4.3 The unit cell for this new compound is orthorhombic, with the dimensions a = 3.030A, b = 13.18A, c = 2.986A7 V=119.2A.' Table I lists the X-ray diffraction data for V.3,.

Jan 1, 1957

By E. O. Fromm, R. I. Jaffee, R. M. Evans

IN connection with a research on gallium alloys, a method for the thermal analysis of very low melting alloys was developed, which appeared to be worthy of more than passing interest. As used, the method was suitable for work in the temperature range, — 72° to 250°C. However, with suitable adjustment, the method could be adapted for use over broader temperature ranges. The Rosenhain temperature gradient furnace,' adapted for low-temperature use, was the basis for the method. The gradient was set up in a stainless steel tube. The specimens were lowered through it at a constant rate while time-temperature or inverse rate data were taken. It was essential to maintain careful control of the top and bottom temperatures of the gradient. Also essential was good heat transfer from the walls to the specimen. This was accomplished by a liquid heat-transfer medium.

Jan 1, 1953

By P. Barnes

Several interesting and important considerations may be based upon an analysis of the cost of producing Bessemer rails, and the facts thus set forth may be much more clearly emphasized by re ducing each item of cost to its own fractional proportion of the sum total in each branch of the manufacture. The estimate given below is not absolutely complete in minute ness of detail, but it may be fairly taken as a basis for the suggestions to be noted : Perhaps the most striking comments that can be made upon this statement are those arising from a consideration of some of the smaller items, and even the least of these quite loses its insignificance when its proportion of the whole is expressed in actual money, as for the work of a year, or even for a single day. Thus, if the item as be considered, the importance can be clearly

G. H. CLEVENGER, Colorado Springs, Colo.-Mr. Crowe's paper will be of great interest to cyanide operators, as it is a distinct new development in cyanidation. After reading the paper it occurred to me that some of us had done practically the same thing some time ago, but without design and unconsciously. I refer particularly to the operation of some of the earlier types of vacuum filter, used in connection with a dry vacuum pump and a receiver, which is somewhat similar equipment to that employed by Mr. Crowe. However, we did not appreciate the good effects we were getting from such of this solution as was precipitated, and it has remained for Mr. Crowe to bring distinctly to our attention the advantages of removing air from cyanide solutions before precipitation. Full credit is therefore due him for this very clever improvement in the cyanide process.

Jan 11, 1918

By Paul T. Allsman

Recently the U.S. Bureau of Mines completed organizational changes that, for the first time since the beginning of World War 11,. re-emphasize mining research as an important part of its responsibilities. A progress report follows on the Bureau's improved program for mining research. During World War II the Bureau's mining research lapsed in favor of short-range, more urgent activities. Since the end of the war mining has grad- ually returned to an economy where reduced costs and increased efficiency are essential to a vigorous industry, and demand for improvement through expanded research is again pre-eminent. In recognizing this situation, the Bureau is again emphasizing mining technology and has reinstituted some of its earlier mining research activities. Recent research, however, follows a more scientific approach in solving mining problems because new technology, particularly new instrumentation, has developed rapidly during the past decade.

Jan 7, 1960

At the annual meeting of the American Society of Mechanical Engineers, Dec. 4 to 7, 1917, a great many matters were discussed and acted upon in which nearly all engineers are equally interested. Of the numerous sessions of the meeting, only a few of the most important can be referred too here. The Committee on Gages held an open meeting for the discussion of this important matter. Representatives from a large number of manufacturing plants and from several departments of the Federal Government were present. The question of gages and standardization of mechanical details is of course of paramount interest just now in connection with the manufacture of ordnance and ammunition. After discussion, the following recommendation was adopted by the meeting, for inclusion in all Government contracts for the manufacture of these materials. The maste and reference gages and standards of measurements, with which Ore

Jan 1, 1918

By A. D. Bryant

APPROXIMATELY 2 1/2 million tons of silica sand and ground silica with a value of $7.25 million is produced annually from the Ottawa, Illinois, district. These silica products come from the well known St. Peter sandstone formation which covers part of the Mississippi Basin extending from St. Paul on the north to the central part of Arkansas on the south and from Muncie, Ind., on the east to Kansas City on the west. Practically the whole state of Illinois is underlain by this formation except where removed by erosion. Sand produced from the St. Peter sandstone in the Ottawa district is noted for its purity, uniformity, and quality. In addition to various screened grades for industry about 10 pct of the total production of the Ottawa district is ground into silica flour for use in glass, abrasives, enamel, porcelain, tile, for foundry and filter sand, and other uses.

Jan 3, 1953

By H. E. Howe, A. A. Smith

E. Schumacher.*—Mr. Smith has shown us once again how variable lead alloys can be. I have studied lead alloys for a good many years and know from experience that their behavior cannot be predicted by analogy with other alloys. I have always been interested in observing how the creep resistance of lead may be improved by the addition of as little as 0.03 per cent Ca. Without the presence of calcium the grains of extruded lead pipe are fairly equiaxed and motion can take place easily at the boundaries. The calcium addition of 0.03 per cent causes the grain boundaries to become very irregular and jagged, and results in creep resistance many times greater than that of pure lead. Mr. Smith showed that in the one per cent antimony-lead alloy creep is occasionally excessive even where low stresses are involved. We have observed this phenomenon many

Jan 1, 1945

By Guy T. McBride

The 1970's have been considered a pivotal decade for the mineral industries. Undergraduate mineral engineering education is relevant to this theme; in particular, there are three interrelated problems: 1) The goals, and therefore the course requirements, of the under- graduate curricula are in question; 2) The unit costs of undergraduate education appear excessive to those who bear the charges; and 3) The present social ambience detrimentally affects the work attitudes and career motivation of both prospective and in-course students. Any discussion of these problems must bottom upon recognized national needs for minerals and a technologically sound minerals industry staffed by competent engineers, particularly at the exploration, development and production levels. Fortunately, these needs have been recognized and to some extent quantified, and they are even now under further intensive study by some of the most competent members of society and the profession.

Jan 3, 1973

By D. W. Fuerstenau

The United States is rapidly approaching an acute shortage of minerals. According to some observers, this situation may even be more severe than the energy crisis because the US consumes nearly 30% of the world's mineral production. With the mounting competition for world mineral supplies, we can no longer take for granted that foreign mineral products will be available to the US as abundantly as in the past. In 1973, US consumption of mineral raw materials was $35 billion. Of this, $7 billion consisted of imports. Without a drastic reorientation towards the mining of domestic mineral resources, the 1973 $7 billion deficit might mushroom to $100 billion by the year 2000. Thus, a return to domestic sources of raw materials will become absolutely necessary-and will be bucking the trend of the past 25 years, characterized by capital investment for growth in multinational overseas mining operations.

Jan 11, 1975