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By G. G. Campbell

The Bureau of Mines in cooperation with Quaker State Refining Corp. conducted two underground-combustion oil-recovery experiments in the Venango Second sandstone in the Reno pool, Foster-Rena-Oil City field, Sugar Creek Township) Venango County, Pa.) to determine the applicability of the process for reservoirs producing Pennsylvania-grade paraffin-base crude oil. Tests were terminated when analyses of produced gas showed that a self-sustaining combustion front did not exist. It was thought that insufficient fuel had been deposited in the formation. Laboratory retort tests made after the second field test was concluded showed that crude oil from the Reno area would deposit enough fuel to support combustion if air flux, temperature, and time were maintained within defined limits.

Jan 1, 1967

By K. E. Manchester, C. B. Sibley

The feasibility of doping silicon to produce device structres by directly implanting impurity atoms has been demonstrated. Both phosphors and boron ions have been successfully implanted in silicon to produce electrical junctions. Junctions as deep as 1.2 p have been produced by phosphorus ions having energies the order of 80 kev. An electromagnetic separator has been used to controllably produce uniform, large-area implantations for evaluation experimentation. Correlations between junclion depths and ion energies huve been obtained. Orientation effects have been observed and it has been found that the (110) direction is the easy direction for implanting. Monitoring of thermal treatments oj implanted substrates by sheet-resistance measurement indicates a very mild thermal anneal removes most of the damage done during the implantation. These indications are further substantiated by reverse-current measurements of j,inctions Produced by implantation. Electrical characteristics of implanted junctions are compared with those of diffused junctions. We have been interi n the interaction of energetic ions in the III-V groups, in particular boron and phosphorus, with single-crystal silicon to produce type conversion for possible device use. A number of investigators, a few of whom are avies, Kornelson,3 and so forth, have reported on penetration of energetic ions into both amorphous and crystalline solids. While most work has been done with ions of the rare gas and alkali metal groups, some work has been reported by ing, erber,' and others6 in which ions of the 111-V groups have been implanted in single-crystal silicon. A large amount of this work has been done with ion energies in the 100-kev to 1.5-Mev range. An excellent review article has been written by caldin. We have concentrated on ion energies which are in the 10 to 80 kev range, with which over 1500 implanted junctions such as the one shown in Fig. 1 have been produced in silicon substrates with both phosphorus and boron ions. Fig. 1 is a 3-deg angle lap in which the n type area produced by 66 kev P is delineated and the junction is 9500A below the surface. EXPERIMENTAL Implantations reported in this paper were made with the ion source adjusted to produce ion currents in the range of 1 to 2 pa with accelerating voltages varied from 10 to 40 kv. When using doubly charged ions this produced 10 to 80 kev ions. This allowed substrate temperatures to remain below 100°C. Sam- ple movement resulted in beam impingement angle variation of 7 deg from the normal to the substrate surface. Substrate resistivities have been varied through the range of 0.001 to 500 ohm-cm and specimens oriented in three directions, (110), (Ill), and (loo), within 12 deg. RESULTS For the purpose of this paper, discussion of results will be limited to phosphorus implantations with mention of results for boron-implanted silicon. Similar results have been obtained for boron and will be reported at a later date. In Figs. 2, 3, and 4 depth penetration is shown

Jan 1, 1967

By Murray Weintraub

In an investigation of the incineration of combustible wastes, the Bureau of Mines studied the effect of dimensional parameters, process variables, and fuel properties on the operation of an incinerator that consisted of a single cylindrical combustion chamber in which all combustion air was supplied tangentially above the fuel. Construction and operation of three designs of such a device proved that the tangential overfire air design is effective in providing efficient combustion and low concentration of particulate matter in the effluent gas. A correlation was found that related burning rate with air rate, chamber diameter, and inlet port diameter. In one of the incinerator models, ignition was by radiation from a preheated surface. The temperature of this surface was required to be 1,400° to 1,600° F to insure ignition of moist refuse; however, this had little effect on combustion rates. In the combustion of moist refuse, evaporation of the water proceeded through the fuel bed as a wave, with an ignition wave following the evaporation.

Jan 1, 1967

By Henry M. Harris

A study was made by the Bureau of Mines to determine if shapes of oxide-glass compositions could be roll-formed at high temperatures, and to find the conditions required for adequate formability. A unit with directly connect' furnaces and heated rolls that allowed forming of most of the compositions developed. Glasses of the feldspar type were chemically unreactive with the alumina grains, and allowed the best roll forming. Optimum forming was attained at temperatures of 1,400° to 1,530° C, with compositions containing 30 or 40 percent feldspar and 60 or 70 percent alumina. Formability was better when compositions contained minus 325-mesh materials, rather than coarser or finer powders. In many cases, roll-formed shapes had physical properties equal to or better than the normally sintered shapes of the same composition.

Jan 1, 1967

By Frank A. Peters

An evaluation is made of a lime-soda sinter process for extracting alumina from clay. In this process, alumina is extracted by sintering clay with soda ash and limestone and then leaching the sinter with a dilute sodium carbonate solution. The sodium aluminate solution formed during leaching is separated from the residue and treated with lime in autoclaves to remove dissolved silica before alumina trihydrate is precipitated with carbon dioxide. The tri-hydrate is then calcined to a-alumina. Two options, dry grinding and wet grinding, are used in the sintering step. The fixed capital costs for plants producing 1,000 tons of alumina per day are $72 million for the dry grinding option and $66 million for the wet grinding option on a Marshall and Stevens chemical equipment index basis of 240.0. Specific geographic locations of plant and raw material sources are not assigned, but, since this process requires large quantities of both lime-stone and clay, the plant site is considered as variable with relation to the clay mine and limestone quarry. A nomograph is given to find operating costs at various delivered costs of clay and limestone. If the plant is located nearer the limestone quarry so that the delivered cost of clay is $2 per ton and the delivered cost of limestone is $1 per ton, the operating costs are $76.47 and $71.61 per ton of alumina for the dry grinding and wet grinding options, respectively. On the other hand, if the plant is located nearer the clay mine so that the delivered cost of clay is $1 per ton and the delivered cost of limestone is $2 per ton, the operating costs are $80.15 for dry grinding and $75.34 for wet grinding.

Jan 1, 1967

Jan 1, 1967

By Driver R. C, Moelle K. H R

This paper is dedicated to the memory of our friend Peter McKenzie who contributed much to the knowledge of the New South Wales Coalfields.ABSTRACTA fossil river system was recently mapped over parts of the Southern Coalfield, N.S.W. This river system occurs in the roof strata of the Bulli Seam. Sandstone of a fluvial nature was deposited in its course. The sandstone exhibits strong sedimentary vectorial properties and has a marked influence on strata-control in colliery workings.The sedimentary features analysed indicate an approximate S200W flow direction. Petrological studies reveal a clastic, well-cemented sedimentologically and structurally anistropic rock type. Washouts have been found and isopach maps of both sandstone and underlying roof-strata have been compiled. Relevant measurements were carried out in existing colliery workings and on bore cores.Optical determinations of feldspars revealed the presence of plagiocIase feldspars with few exceptions. Most of the feldspars are altered to clay minerals. It was found that a geographical trend exists in the distribution of feldspars, with more basic plagioclase in the northern part of the field.The source area of the fluvial sandstone lies to the north of the Southern Coalfield.Petrofabric analyses were done on several specimens of the fluvial sandstone. In the vicinity of major disturbances, penetrative fabrics were discovered.Calcites (e, 0112), micas (001), and quartz (crystalIo graphic c) show preferred orientations.

Jan 1, 1967

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By Matthew J. Sheridan

The Bureau of Mines study described in this report was conducted in the Denver, Colo., area (1) to summarize existing conservation practices as related to the most beneficial utilization of deposits of sand and gravel; (2) to identify the conflicting positions of the aggregate producer, the mineral owner, nearby residents, and local government officials responsible for determining land status and for issuing operating permits; and (3) to show the need for planning in Denver and in other expanding communities toward obtaining the benefits of conservation of our rapidly dwindling mineral resources. In order to determine the effects of urbanization on the Denver aggregate industry, interviews were held with owners of sand and gravel operations, with producers of concrete and bituminous pavement, with city and county planning and zoning personnel, and with representatives of various interested organizations. The conservation and ultimate utilization of deposits of construction raw materials near expanding urban areas can best be accomplished by long-range land-use projection and the requesite cooperation of technically advised planning and zoning administrators, government officials, mineral producers, and land developers.

Jan 1, 1967

Jan 1, 1967

By J. B. F. Champlin

The continuing development of the nuclear industry in the United States requires a program of waste disposal that insures against the release of large amounts of radioactivity to the environment. This paper describes research on one proposed means of disposal of this waste, that of injection into geologic formations at depth. Nuclear production plant wastes were simulated and injected into samples of sedimentary rock obtained from outcrops, quarries, and deep wells. Changes in the chemical and physical characteristics of the rocks caused by the interaction of ions and suspended particles in the waste solutions with the cementing material and claylike particles in the rock are discussed. Laboratory tests show that nuclear wastes can be injected into many natural porous, permeable geologic formations. Injectivity can be maintained over a longer period by monitoring the ionic balance and particle-size distribution of waste streams. The combination of permeability and porosity with low cation-retention capacity, as exhibited by most sandstones, would satisfy the engineering requirements for the subsurface disposal of nuclear waste. Shales and clays with their low permeability and high cation-retention capacity would make excellent confining formations. The amount of cation retained by sedimentary rocks increases with increasing valence or concentration of the cation or decreasing brine concentration. The use of rock cores as model reservoirs had proved successful in determining some of the parameters that need to be considered in full-scale field disposal of wastes.

Jan 1, 1967

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By D. W. Bacon

Plant process optimization programs are often costly, both in technical effort and loss of production. Evolutionary Operation or "EVOP" is a mode of plant operation consisting of controlled cyclical changes in process conditions by which information is provided concerning potential process improvements while both volume and quality uniformity in production are maintained. Its conceptual simplicity and low cost of utilization have led to successful adoption in a variety of industrial manufacturing operations. This paper is an expository account of basic EVOP theory, the problems encountered and the organization required in applying it to a processing plant. Illustrations are provided which indicate the payoff that can result.

Jan 1, 1967

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,' or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967

By Manuel Gomez

Low-temperature carbonization product yields for 129 coals representative of 12 Utah coalfields were estimated, using regression equations developed from heating value and proximate and ultimate analysis data. It was shown that yields of char, tar plus light oil, water of decomposition, and gas, as well as the gas volume and the heating value of the gas, could be predicted with reasonable accuracy. Published and experimental results from eight Utah coals carbonized at selected temperatures in the 4500 to 1,000° C range were used to determine the effect of temperature on product yields. Carbonization temperature, heating value) oxygen, and volatile matter of coal appear to be the principal variables influencing carbonization product yields. Data presented show that the heating value and the residual volatile matter in low-temperature char may be predicted using relationships developed from proximate analysis data for 220 coals.

Jan 1, 1967

By J. L. Shultz

Mass spectrometric analyses were obtained for naphthalene and anthracene oils, heavy creosote, and three fractions of a pitch. The average molecular weight, aromaticity, and mean structural unit were determined for each fraction. The investigation of these fractions of coal tar has resulted in semiquantitative data for 38 structural types and carbon number distribution data for their alkyl derivatives. The molecular weights of 10 of these structural types indicate ring systems not previously reported in products from high-temperature carbonization of coal. Two of these structures are poly-nuclear aromatic hydrocarbons, two are oxygen-containing compounds, one contains sulfur, and five are nitrogen-containing compounds.

Jan 1, 1967

Jan 1, 1967

By Adrian C. Dorenfeld

[Agitation and transport of slurries have been investigated intensively for the past twenty years. It has been shown (1) that slurries have the properties summarized in Figs. 1, 2, 3, 4, and S. For a detailed exposition the reader is referred to the above reference and the bibliography, which, in turn, have extensive references and bibliographies. An interesting problem with which the senior author has been concerned with is the scab up of power requirements for slurry agitators operating in the laminar region with pseudo plastic materials. Pulps of shaly ores, after various chemical reactions in aqueous leaching systems, are often difficult to settle and filter if agitation is violent. In these cases agitation must be at a minimum, yet prevent [tling] such as in copper uranium ores. This mild agitation is on the laminar region.]

Jan 1, 1967

By Ralph L. Merklin

One of the most commonly employed set of calculations in mill design and research is the material balance, known in wet beneficiation plants, as an Ore and Water Balance. For mill designers, the balance is one of the principal requirements in determining the proper size of launders, pipelines, process equipment, etc. In process development, one of the major goals is the establishment of an optimum balance. The usual procedure for calculating a material balance involves a manual technique utilizing reference tables, pre -obtained data, and a slide rule or desk calculator. With these, the engineer must perform a series of calculations which are repetitious in nature and time consuming. Figure I is the flowsheet of the grinding and flotation circuits for a copper concentrator. The initial ore and water balance was calculated manually and required approximately 24 manhours. Later, a number of changes were made in the balance, each of which required an average of 8 manhours.

Jan 1, 1967

By Clyde M. Pearce

This paper describes the facilities at Pointe Noire, Quebec that Wabush Mines utilizes for the receipt, distribution, stockpiling and shipping of iron ore concentrate and pellets. The main topics to be covered will be: 1. - General description 2. - Concentrate receiving facilities 3. - Conveying circuits 4. - Stockpiling 5. - Vessel loading GENERAL DESCRIPTION The map of the eastern Quebec - western Labrador area as shown in Appendix #1 shows the location of Wabush Mines properties. You will note the Scully Mine located at Wabush Lake, Labrador, 235 miles north of the town of Sept-Iles, Quebec. Our neighbors, the Iron Ore Company of Canada have their properties further north at Shefferville, near by at Carol Lake and at Sept-Iles. To the Southwest, our other neighbors, Quebec Cartier Mining, have their iron ore processing facilities and their terminus on the St-Lawrence at Port Cartier. Concentrates are prepared at the scully Mine by mining, crushing, grinding, concentrating, drying and high tension separation for shipment by rail to Pointe Noire, Quebec. Pointe Noire is situated across the bay from the town of Sept-Iles, Quebec on the North Shore of the St-Lawrence River. The concentrate consists of 66% iron, 2 ¼ percent silica and practically no moisture, permitting the use of specially constructed railroad cars and handling facilities to convert the concentrate into pellets, the final product.

Jan 1, 1967