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By Robin P. Gardner

A radioisotope tracer method combined with a suitable back-calculation method is proposed and evaluated for the determination of model simulation parameters in open-circuit continuous ball mills. The method essentially consists of using impulse and/or step injections of short-lived radioisotopes of the naturally occurring trace elements manganese and sodium. It is evaluated here on the basis of the minimum standard deviations of the product weight-size distributions. These minimum standard deviations are taken as those predicted by a Poisson distribution of the number of particles present in size fractions of the samples taken for analysis. Previously developed tanks-in-series lumped parameter models are used in the evaluation. The results indicate that the method is very promising.

Jan 1, 1976

By H. J. Polta, R. W. Michelson

Discounted cash flow analysis is commonly used to evaluate the profit making potential of a business venture. The same method can be used to analyze the effects of varying physical and economic conditions upon the real cost of supplying a mineral commodity. If a fixed rate of return on a capital investment is specified, and the flow of cash, discounted at that rate, is just adequate to repay the investment over the life of the venture, the net present value of the venture is zero. At this condition it is possible to evaluate the unit cost of producing the mineral. It will be exactly equal to the selling price required to calculate a zero present value. Increasing a particular cost factor will not always increase the cost of supply by the same amount. For example, in iron production from magnetic taconite, an increased cost per ton associated with beneficiation would be integrated into the discounted cash flow model along with local, State, and Federal taxes, depletion and depreciation allowances, resultant increased unit recoveries, and all of the other related component cost factors. Rather than adding to the cost, the factor may have a positive, instead of a negative, effect on the discounted cash flow and cause a decreased cost of supply. This value can be determined by a computer model which iterates the necessary selling price until the net present value is essentially zero. The discounted cash flow evaluation model lends itself particularly well to an application of the Monte Carlo simulation method for calculating a probability distribution of iron unit cost resulting from the probability distributions of the component cost factors.

Jan 1, 1969

By Marc Lemieux

Computer pit design techniques generally make use of models in which the deposit is represented by a regular array of data. Using a regular system, the number of data points required to represent the air, waste and mineralization in a large deposit become excessive. The number of blocks used to describe the deposit is dependent upon the block size. The quality of the pit wall slope design also is dependent upon the block size used and the method of defining the slope. The error associated with reserve calculations becomes greater with increasing block size. A deposit model consisting of variable sized air and mineralized blocks has been developed at the University of British Columbia and improved upon at Climax for pit design work. The method permits put- ting the entire model in core for rapid data processing. This permits the use of a versatile cone generation technique which allows close adherence to variable slope constraints in all directions. The conical shape is approximated by rectangles on each level which equal the area of the ideal conical intersection. The shape of the intersection may vary from approximately circular to elipsoidal. The approximate cone shape is controlled by the slope constraints applicable at the point of intersection on the bench. The overall modeling technique greatly assists the pit design engineer in developing a high quality pit design.

Jan 1, 1977

By Paul R. Wieber, Atam P. Sikri

This paper describes the U. S. Energy Research and Development Administration's (ERDA) program to develop in situ coal conversion processes, especially gasification. The potential of this technology, the technical directions being explored, and the program strategy to carry the process concepts toward commercialization are emphasized. The geographic location of the U. S. coal resources and a market analysis are described. Commercially successful in situ coal processes could add over a trillion tons of coal to the U. S. coal reserves. The economics of these processes is compared with surface gasification. Independent studies show this process to be 25% cheaper than surface gasification for Western coals. The major projects are briefly described. The Linked Vertical Well process is in the most advanced stage and shows great promise. The last test produced a low-Btu gas averaging 171 Btu per standard cubic foot for average production rates of 8.5 million standard cubic feet per day. The other projects are Packed Bed, Longwall Generator, and Steeply Dipping Beds. Unique factors of the process development are discussed which may lead to commercial processes in the near term. A development strategy is proposed by which this technology could be commercialized before 1983 with potentially lower gas prices and lower environmental impacts, relative to mining plus surface gasification.

Jan 1, 1979

By N. Rowlands, J. A. Finch, R. Espinosa-Gomez

The sulphation roast-leach process for complex sulphides results in phase changes due to roasting and leaching. The phases in the calcine, and in the neutral and hot acid leach residues were identified and their degree of liberation determined in order to design and Interpret separation tests on the residues. The hot acid leach residue was composed of hematite, silica, and lead sulphate with some associated silver. Magnetic separation was selected as the process for producing a lead concentrate, as the non-magnetic product. Separation was limited by -1 pm hematite reporting to the product, and hematite/lead sulphate agglomerates reporting to the magnetics.

Jan 1, 1984

By Chi-shing Wang

Recently the U.S. Bureau of Mines has undertaken a research project to develop the mechanical roof pulling technique as a method for evaluating the effectiveness and the comparative advantages and disadvantages of various roof bolting systems for underground coal mines, based on the characteristic responses of bolted mine roofs to a prescribed external loading system. Two preliminary experiments of the test method were conducted in the Bureau's Safety Research Coal Mine (SRCM) at Bruceton, Pa., and further trials are underway. The fundamental concept of the test method, the design of test rigs, and the experimental results are summarized in this progress report.

Jan 1, 1976

By M. Paulus

It is known that multicomponent powders are mostly nonhomogeneous. This paper investigates the effects of nonhomogeneity of composition and grain size on the melting point and the sinterability of compact taking into account homogenization mass transport and the length of the diffusion path in solid state sintering, and the kinetics of liquid phase formation in liquid phase sintering. After a discussion on the ideal characteristics of a powder for sintering and low temperature reaction, the main conventional processes are compared. Finally we develop the freeze-drying technique and demonstrate the capabilities and the limits of the process by some examples, mainly in the ceramics field.

Jan 1, 1980

By Rex B. McLellan, W. A. Oates

FROM a consideration of the application of the Gibbs-Duhem equation to multicomponent systems arken' derived the following equation applying to dilute solutions of a solute, 2, dissolved in a binary solution, 1-3:

Jan 1, 1969

By Andrew E. Nevin, Sidney A. Williams, James N. Lukanuski

Three porphyry copper districts in southern Arizona are partly overlain by post-ore fanglomerates with certain physical and petrologic characteristics which define a distinct and significant class of rock. These units are the Locomotive fanglomerate at Ajo, the Helmet fanglomerate at Twin Buttes-Mission-Pima, and the Cloudburst formation at San Manuel- Kalamazoo, herein termed “Locomotive-type fanglomerates.” Post-ore units at Poston Butte and Lakeshore, Ariz., and Sar Chesmeh, Iran, also appear to fit this class. Locomotive-type fanglomerates may be genetically related to porphyry copper deposits as subsequent products of differentiation, volcanism, uplift, and sedimentation in short-lived basins of limited areal extent. These units are sufficiently distinct to be utilized as exploration guides for porphyry copper deposits in the Southwestern U.S., northern Mexico, and elsewhere.

Jan 1, 1977

By R. C. Mahon

THE Homer iron-ore mine is at Iron River, Mich. Because it covers a large area, 400 acres, and because there was a considerable depth of water in the glacial drift above most of the ore bodies, this mine has presented a number of unusual and often difficult operational problems. The purpose of this paper is to discuss a few of the most important problems encountered. SURFACE WATER Mining on this property was started on one 40-acre tract. The ledge in this area was the highest on the property and, although it was a real problem, water could be handled by underground pumping. During the first period of mining, drifts were driven just under the ledge and holes were drilled through to the surface material. In later years these drifts have been extended wherever possible. Although these drifts assisted in the drainage problem, it was evident they would not be sufficient alone. Before mining on a large scale could be started on this property, the water problem had to be solved. A number of test holes were put down to the ledge, and showed that there was an average 150 ft. of water-saturated glacial drift above the ledge over the rest of the mine. The upper 70 ft. was gravel and sand and the lower 80 ft. clay and hard pan, with some narrow seams of sand and gravel. It was evident that the water above the clay seam could not be drained off through openings in the ledge and for that reason it was decided to install surface drainage wells. This method of drainage was entirely new at that time and was pioneered at the Homer mine. The sinking of the first well was started in June 1929. Immediately following the first well a number of wells were sunk, but only to the top of the clay seam. This was done with the idea that a greater capacity could be obtained in a shorter time from gravel seams where the water flowed more freely and that the cost of pumping the water above the clay seam would be considerably less than if the wells had all been sunk to the ledge at once. Before the drainage of surface water was started, 1200 gal. per min. against a head of 800 ft. was being pumped from the mine. By March of 1932, with five surface wells in operation, the mine pumping had been reduced to 150 gal. per min. At this time we were pumping 5000 gal. per min., under an average head of 110 ft. from the surface wells. The total pumping costs were 30 per cent less than in 1929 because the greater capacity was being pumped at a much lower head. From 1932 to 1936 the mine was idle and all surface pumping was stopped. Since 1936, 10 new wells have been added with a total pumping capacity of 8000 gal. per min. at the present time. The water level has been lowered 70 ft. since surface pumping was started in 1929, and it is now approximately at the top of the clay. To remove the water below the clay seam, 11 of the 15 wells were sunk to the ledge.

Jan 1, 1945

By M. Karfakis, K. Kim, R. V. de la Cruz

The in situ deformability of a closely jointed basalt rock mass was determined by two different methods: the NX-borehole jack method where displacements of opposing curved platens were related to applied hydraulic pressures, and the modified Goodman jack method where tangential strains on the borehole walls were related to induced tangential stresses. The modulus obtained by the modified Goodman jack method were much higher than those obtained by the NX-borehole jack method. To explain the discrepancy, the influence of fractures and test variables, such as depth, orientation, hole location, and applied pressure on the calculated modulus of the rock mass, were analyzed by factorial analysis. It was found that the orientations and measurement depths have statistically significant effects. The in situ deformability values obtained by nonlinear regression analysis were also found comparable with other measurements and empirically predicted values for the basalt rock mass.

Jan 1, 1984

By Charles Goodale

With notes on other mines of the Marysville district by WALTER McDERMOTT, London, England, and F. L. Sizer, Dos Cabezas, Ariz. (Salt Lake Meeting, August, 1914) THE purpose of this paper is to review the history of the Drumlummon, one of the famous old mines of the West. Mining engineers, when sent to examine new mines in old districts, or to decide whether an old property, under new conditions, will pay to re-open, have had difficulty in learning anything authentic regarding workings which are under water, and historical facts about the working character of the ore, the total production, and the value of the ore with increasing depth. Not many years elapse after the pumps are pulled, before maps, books and records are destroyed, and the value of the publications of the Institute would be increased if they contained the history of many old mines now abandoned. The unsuccessful efforts of the writer quite recently in trying to obtain reliable information about a gold mine which was reported to have produced several million dollars between 1880 and 1888, the workings of which are now partially caved and under water, impressed upon his mind the desirability of having a permanent record of old properties. In this particular case, the owners insisted that under present conditions of improved methods of treatment -particularly by the use of cyanide, which was not an applied process when the mine was operated, the property. could be made to pay a handsome profit on ore left in sight in the old workings, but no assay records could be found to confirm these assurances, and even the records of bullion shipments had been destroyed. If surveys and maps were made as the work progressed, no trace of them could be found, and therefore opening of the ground through a new shaft and drifts therefrom would be attended by some risk while exploring near the old workings. Fatal accidents by flooding under these conditions have occurred, and as an evidence that miners have fears of such dangers, it was urged upon the Mining Committee during a recent session of the Montana Legislature, by a delegation of

Jan 8, 1914

Prospecting methods used in Tennessee have gradually improved with the years, as required by depletion of the easily accessible and shallow deposits and the universal trend toward mechanization, and as necessitated by exploring deeper beds, often occurring under limestone and flinty overburden. In the early days it was a very simple matter to dig pits by hand, using a plentiful supply of local farm labor to expose relatively shallow deposits of "brown rock" under shallow clayey overburden that would stand up without timbering. Visual inspection of the exposed phosphate and expert judgment of the "grade" analysis, aided by a "biting" test to reveal presence of unwanted silica, furnished most of the information required. All this might be helped by a few samples sent to the local chemist† who supplemented his income by judicious trading or tanning a few bear skins. The extra curricula activities did not affect the accuracy of the analysis which hold up even under present day standards. Some shot and core drilling was done in Hickman County, mostly for the limestone-like blue Phosphate deposits. The next step was the use of a 4-in. posthole auger, hand operated as described by Guenther, followed by a completely mechanized rig, as described by Pickard. Both these methods are practically adapted to the prospecting of the relatively soft brown rock deposits at moderate depths of clay overburden. For prospecting in areas of deeper overburden, such as are often found in Hickman County, up to 150 or even 200-ft depths, a modified core-drilling method is described by Guenther. Johnston describes a special diamond-drilling technique, developed by TVA, to penetrate flint horizons, which was adopted by the International Minerals in chemical corporation to prospect in Hickman County where deposits had previously been prospected at considerable expense and with difficulty, by small, temporary, hand-dug shafts.

Jan 1, 1948

Prospecting methods used in Tennessee have gradually improved with the years, as required by depletion of the easily accessible and shallow deposits and the universal trend toward mechanization, and as necessitated by exploring deeper beds, often occurring under limestone and flinty overburden. In the early days it was a very simple matter to dig pits by hand, using a plentiful supply of local farm labor to expose relatively shallow deposits of "brown rock" under shallow clayey overburden that would stand up without timbering. Visual inspection of the exposed phosphate and expert judgment of the "grade" analysis, aided by a "biting" test to reveal presence of unwanted silica, furnished most of the information required. All this might be helped by a few samples sent to the local chemist† who supplemented his income by judicious trading or tanning a few bear skins. The extra curricula activities did not affect the accuracy of the analysis which hold up even under present day standards. Some shot and core drilling was done in Hickman County, mostly for the limestone-like blue Phosphate deposits. The next step was the use of a 4-in. posthole auger, hand operated as described by Guenther, followed by a completely mechanized rig, as described by Pickard. Both these methods are practically adapted to the prospecting of the relatively soft brown rock deposits at moderate depths of clay overburden. For prospecting in areas of deeper overburden, such as are often found in Hickman County, up to 150 or even 200-ft depths, a modified core-drilling method is described by Guenther. Johnston describes a special diamond-drilling technique, developed by TVA, to penetrate flint horizons, which was adopted by the International Minerals in chemical corporation to prospect in Hickman County where deposits had previously been prospected at considerable expense and with difficulty, by small, temporary, hand-dug shafts.

Jan 1, 1948

By James M. Schopf

Gilbert H. Cady (Senior Geologist, Head of Coal Division Emeritus, Illinois State Geological Survey, Ur-bans)— Those coal mining and preparation engineers and operators who read this article will probably be most concerned with those parts which deal with the applied aspects of coal petrology in the fields of mining and technology. Actually the two categories overlap to such a degree that they are essentially one. The article appears to suggest that there are two points of veiw in the field of applied coal petrology. From one viewpoint the interest is in the attributes of the various macerals (Fig. 4)—vitrinite, exinite, and inertinite—-in terms of utilization (when the coal is burned, coked, gasified, hydrogenated, etc.). From the other point of view, assuming that the macerals do possess individuality in behavior, interest attaches to the possibility that coal of a particular type (maceral composition) can be prepared by discriminating methods of preparation and blending. Most of the 29 items listed for mining and technology can be assigned to one or the other of these two categories. Somewhat the same simplicity that resides in the items of the proximate chemical analysis is desirable for the petrologic analysis. This simplicity appears to be fairly well achieved by the group maceral device provided mineral matter is also included. At present, without fully adequate experimental substantiation, the three types of material represented by the group macerals vitrinite, exinite, and inertinite are regarded as sufficiently different in composition and properties so that the preponderance of any one type gives the coal distinctive properties provided it is not too high in rank. This appears to be increasingly true with coals of decreasing rank from medium volatile bituminous coals downward. The article reflects the great emphasis placed on the technique of descriptive coal petrology in America. Such description has resulted in a good understanding of the nature of the fundamental variability in the physical composition of bituminous coals. Such understanding has been attained very largely by the thin section technique used in coal bed profile analysis introduced by R. Thiessen after the manner suggested by the data assembled in Table 11. In contrast, the group maceral concept of coal analysis in terms of the categories indicated on the left hand side of Fig. 4 is particularly useful for broken coal analysis and applied coal petrology, in which evaluation is largely based on quantitative concepts. It is inadequately emphasized in this article that although the Thiessen procedure is suitable for the purpose of petrologic description in which texture and orientation are of critical importance, it is less well adapted to the technological uses of applied coal petrology. No doubt those persons whose interest may have been aroused in the possibilities of more refined coal preparation by this and other recent contributions to the literature of coal petrology will understand that certain technical aspects of coal petrology, particularly in the field of descriptive petrology, are still a matter of some controversy among the coal petrologists, but they will also appreciate that Schopf has made an important contribution to the field of coal petrology in America by pointing out that such petrology requires consideration of disoriented or broken coal samples and that results are expressed less in descriptive terms than in quantitative values with respect to the four types of material composing coal—-vitrinite, exinite, inertinite, and mineral matter. Unfortunately because so much American coal petrology has been descriptive of the coal in the bed there is a dearth of literature on applied coal petrology. Research and experimental data in this field are greatly needed.

Jan 1, 1959

By Theodore P. Holt

The Mines Operating Co.'s plant at Park City, Utah, was designed to treat the low-grade fillings in the old stopes of the Ontario mine. These fillings carry 6 to 14 oz. of silver, 1 to 2 lb. of copper, 0.01 to 0.015 oz. of gold, and a small percentage of lead and zinc. The treatment consists in mixing the crushed ore with coal dust and salt and then roasting in a new type of furnace by combustion of the contained fuel. The roasted ore is leached with an acid salt solution to dissolve the silver, gold, copper, and lead. At present these metals are precipitated together on scrap iron and the product sold to a refinery. The only new feature of importance in this scheme of treatment is the roasting process, which makes possible the chloridizing of ores without any loss of the valuable metals, and at a very low cost. History of the Development of the Process The roasting process- had its beginning in connection with research work at the Utah State School of Mines. N. C. Christensen, Jr., who held one of the School of Mines' fellowships, was engaged in some experimental work on blast roasting. At the same time I was doing some work on the insoluble gold in Mercur base ores. Mr. Christensen roasted some of this base gold ore in his pot furnace, and found that when he mixed a sufficiently low percentage of fuel with the ore, it did not sinter but roasted to a leachable product. We considered this a new application of blast roasting, and proceeded to test out a large number of ores in several different types of small roasters which we constructed.. This experimental work continued well into the summer of 1911. In August, 1911, the Consolidated Mercur Gold Mines Co. installed a small roaster of our design, which we proposed to operate on the counter-current principle, feeding mixed ore continuously on top, and at the same time drawing off the roasted ore from the bottom. By proper adjustment we hoped to maintain a permanent roasting zone near the center of the column, the ore moving downward as roasted. However, we

Jan 1, 1915

By J. S. Falcone

Soluble sodium silicate materials have well known applications in flotation for desliming, selective depression and corrosion control. Recent advances in the understanding of the complex polymeric nature of silicate solutions using NMR spectroscopy, combined with our studies of the effects of polymeric silicate anions on metal ion activities in solution, oxide mineral surface charges and surfactant adsorption on clays are related to beneficiation processes. The results of these studies indicate the sodium silicates can be used to cause a solution chemistry and particle surface charge characteristics favorable to enhanced effectiveness in typical ore beneficiation systems.

Jan 1, 1983

By W. Bonfield

A study has been made of the dislocation substructures produced in hot-pressed beryllium specimens strained to various levels in the range from 800 x 10-6 In. pev in. to fracture. A number of distinctive dislocation configurations were observed in this region which had not been noted at lower levels of strain. These included dislocation-dislocation interactions to form networks, dislocation "walls", subgrain boundaries and complex arrays, interactions between dislocations and large beryllium oxide particles, and the generation of dislocations from certain particles. The nature of these differences in substructure and their relation to the stress-strain characteristics of polycrystalline beryllium are discussed. In a previous study1 of the plasticity of commercial-purity, hot-pressed beryllium a transition was found in the deformation characteristics in the mi-crostrain region. The initial plastic deformation could be represented by a parabolic stress-strain equation, but above a critical stress there was a complete departure from this relation and a reduction in the strain-hardening rate. The dislocation configurations produced by various levels of micro-strain in this region were examined by transmission electron microscopy and a general correlation was established between the observed transition in deformation characteristics and the dislocation structure of the material. The two stages in the micro-strain region distinguished in these experiments were designated as Stage A' and Stage B'. Stage A' type deformation generally was noted up to a plastic strain of -80 x 10"6 in. per in. and Stage B' type from -80 x 10-6 to -800 x 10'6 in. per in. The discovery of two stages in the microstrain region naturally posed pertinent questions as to the existence of any further distinct stages in the subsequent plastic deformation. The purpose of this paper is to present a study of the dislocation configurations produced in similar beryllium specimens strained to various levels in the range from -800 x 10 in. per in. to fracture and to discuss the relation between substructure and the stress-strain characteristics. It is concluded that this region of strain can be considered as a distinct stage in the plastic deformation of polycrystalline beryllium. Tensile specimens of gage length 1 in. and cross section 0.18 by 0.06 in. were prepared from commercial-purity, hot-pressed QMV beryllium and then annealed at 1100°C for 2 hr. 2 followed by a careful chemical polishing procedure.3 The specimens were strained at a constant rate to various levels of strain in the range from -800 x 10-6 in. per in. to fracture (at 0.5 to 2 pct elongation), using the Tuckerman strain-gage technique1 to measure plastic and total strain. Thin foils were obtained from the strained and fractured specimens by chemical polishing3 and were examined using an RCA-EMU 3 electron microscope. Considerable care waS taken to avoid both accidental deformation during the preparation of the thin foils and excessive heating during their examination. Selected-area diffraction patterns were determined for each micrograph. Tilting experiments were also performed whenever appropriate to establish the dislocation zero-contrast position and hence determine the Burgers vector. This operation was sometimes not possible due to the rapid contamination of the foils which occurred in the electron microscope. RESULTS AND DISCUSSION To enable the distinctions between the dislocation arrays at high and low strain levels to be adequately made, the main characteristics of Stage A' and Stage B' deformation are briefly reviewed. 1) Stage A'. In the annealed starting condition there was a variable density (5 x 107 to 3 x 10' cm per cu cm) of isolated dislocations within a grain. The initial deformation in a tensile specimen was heterogeneous, with the dislocation density increasing in a few grains to 5 x 10g to 1.5 x 101° cm per cu cm. The deformation occurred exclusively on the basal plane by the movement of one or more 1/3 (1130) type dislocation systems. The dislocations were long and regular in form and nearly all the intersections exhibited a simple four-point node configuration. No interactions between glide dislocations and beryllium oxide particles were observed. 2) Stage B. In Stage B' there was a large increase in the number of grains exhibiting dislocation movement and also a change in the nature of the deformation, in which jogged dislocations and elongated loops became the characteristic feature. The splitting up of the elongated loops into smaller loops and the possibility of source action from the re-

Jan 1, 1965

By R. R. Webster, H. T. Clark

I. A. Sirel—I would like to ask Mr. Sims what would the preferred hot metal analysis be as far as manganese and silicon are concerned if you used specially made iron for this process instead of basic iron. C. E. Sims (authors' reply)—A preferred composition would contain somewhat less silicon than the basic pig iron used in these experiments. High silicon requires a large lime addition. Lime must be added in sufficient quantity to neutralize the silica formed and to leave an excess for dephosphorization. Manganese presents almost no problem in operation. It is almost completely oxidized and, in burning, develops considerable heat. The evidence indicates, however, that, in continuous commercial operation, there will be an excess of heat produced, and the bath will need to be cooled in some manner as by the addition of scrap or by utilizing the energy for the direct reduction of ore. There do not seem to be any serious limitations on composition of pig iron. One heat was made with an iron containing 2.27 pct silicon and the phosphorus finished at 0.007 pct. In another, the iron contained 0.45 pct phosphorus which was lowered to 0.019 pct. This indicates considerable leeway in composition. D. R. Loughrey—We are all very much interested in the recent discovery of very large deposits of iron ore both in Labrador and in Venezuela. I would like to ask Mr. Sims if the iron ore at either or both of these places is such that it would lend itself to the manufacture of iron suitable for use in the turbohearth. C. E. Sims-—According to my information, those ores are not essentially different from ores now used in this country for making basic pig. They should, therefore, be adaptable to this process. D. I. Brown—You have spoken about the leeway, or spread in analysis of the various irons you can use in the vessel. I would like to have you tell us, if you can, about the different kinds of steels which can be made in such a vessel. The turbohearth process, or it might more aptly be called pneumatic openhearth, is a little different from that used in most Bessemer shops and in the one in which I worked. If we had a blow in the air over 10 min, the boss was in the pulpit in a hurry

Jan 1, 1951

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.' The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.' and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,' or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969