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By W. D. Douglas, M. J. Hampshire, G. J. C. Young

This paper describes the replacement of a conventional filtration, clarification, and zinc precipitation plant by a carbon-in-pulp (CIP) electrowinning plant, with the objective of improving the recovery of gold from cyanide leached, acid plant calcines. The discussion covers early laboratory studies to the design and erection of the full-scale plant. Particular emphasis is placed on the problems encountered with commissioning and the strategies employed to solve them.

Jan 1, 1985

Iron Ore Resources of the World (Die Eisenersvorrate der Welt)_ By G. Einicke. Verlag Stahleisen, Dusseldorf, 1950. 418 p., with 192 tables and an atlas volume containing 100 p. of reaps. 66 German Marks.-A notable work in which the latest available information on iron ore deposits has been compiled by diligent work, continent by continent, country by country. The author reveals the effect of geological formations, iron content of ore, accessability, cost of transportation, political and economic considerations. Ore beds of importance to the German iron and steel industry are given more space than others. The bibliography contains almost 250 references. A tragic comic feature is the author's complaint that as soon as a map of iron ore resources of a country has been completed, the country's boundaries are changed. Reviewed by W. Trinks, Carnegie Institute of Technology. Industrial Research Laboratories of the United States. National Research Council, Washington, D. C. Ninth Edition. 1950. 445 p. $5.-Contains information on the research laboratories of 2845 industrial and commercial organizations, including names of research executives, location of labs, types of activity, whether any consulting services are offered. There are two appendices, one of which lists data on government labo ratories which cooperate with industry, and the :)ibex naming universities and colleges offering research services to industry.

Jan 2, 1951

Taking advantage of the lessons in administrative organizations which were taught by the war, Director Van H. Manning has put into effect a new form of organization in the Bureau of Mines. The Bureau is divided into two branches, one the investigations branch and the other the operations branch. F. G. Cottrell, who has been chief metallurgist of the Bureau, has been promoted to the position of assistant director and will be in charge of the investigations branch. F. J. Bailey, who has been chief clerk of the Bureau, has been placed in charge of the operations branch with the title of, assistant to the director. All research and technical control will be exercised through the investigations branch, while the non-technical work, administrative duties, and dissemination of the results of the Bureau's activities will be handled by the operations branch. Under the investigations branch comes the division of mineral technology, in charge of Dr. C. E. Parsons; the division of fuels, under the chief mechanical engineer, 0. P. Hood; the division of mining, under the direction of George S. Rice, the chief mining engineer; the division of petroleum and natural gas, under the direction of J. 0. Lewis, the chief petroleum technologist; and the division of experiment stations, under the direction of D. A. Lyon.

Jan 9, 1919

By Claus Guenter Goetzeil

(New York Meeting, February, 1937) The object of this investigation was to determine whether silver alloys could be used instead of the currently employed insert of high-expansion Average Coefficient per Deg. C. over Range 20° to 200° C. Pure aluminum..................................... 24.6 X 10-6 Cast low-expansion Si-Cu-Ni-A1 piston alloy............ 20.0 X 10-6 High-expansion austenitic Cu-Ni cast iron.............. 19.3 X 10-6 Cast steel (0.25-0.35 C, 0.40-1.0 Mn).................. 12.6 X 10-6 Cast iron (3.15 total C, 2.16 Si)....................... 12.8 X 10-6 Pure silver.......................................... 18.9 X 10-6 austenitic ferronickel alloy, to reduce the wear of ring grooves in light metal pistons. A typical example of a piston containing a ferronickel insert is shown in Fig. 1. The high coefficient of expansion of silver made it worthy of consideration, while the small size of the insert would render its use feasible in Germany as an emergency measure. The coefficients of linear expansion of several metals and ailoys are as shown in the table above. Obviously the melting point of the insert must be high enough to prevent it from melting when the light alloy is cast around it. This imposes a lower limit of about 850" C. for the solidus of the silver alloy. Pure silver melts at about 961" C., so that the tolerable depression in the solidus is rather small. To avoid deformation of the insert during use a Brinell hardness number of at least 60 appears necessary.

Jan 1, 1937

By K. Huessener

Discussion of the paper of K. HUESSENER, presented at the New York. meeting, February, .1916, and printed in Bulletin No. -110, February, 1916, pp. 443 to 474. KARL NIBECKER, Youngstown, O.-It has been contended that the method of measuring the operation of a blast-furnace boiler plant by means of the amount of steam generated per pound of coke used in the blast furnace is not of any value and even that it is quite misleading. It has been found, in the plant with which I am connected, that, in general, a blast furnace will operate during a month so close to average. conditions that the average monthly measure of the plant efficiency is indicated by the number of pounds of steam made per pound of coke put into the furnace, neglecting the amount of iron made and the amount of gas used for heating the stoves. For some time, it has been our custom to keep a record of this figure and use it as a general indicator of the operating practice. In comparing this figure from two different plants we have found some difficulty, due to differing conditions. It is conceivable but not altogether probable that a slight difference in burden, kind of ore or coke, would account for this difference. The method of using the gas, whether washed or unwashed, and the plant arrangement, may affect this number. For several plants on which we have worked up this number, we have found that most of the ordinary running irregularities are eliminated during a run of a month or more and that the number is, therefore, satisfactory. In connection with a plot of the number of pounds of steam generated per pound of coke, we are also plotting the production of the furnaces and the pounds of coke used per ton of production. With these three curves plotted on the same sheet, we believe that the operating man has sufficient information to judge of the efficiency of his plant' for any month.

Jan 5, 1916

NOMINATIONS FOR OFFICERS. In accordance with the Constitution, Article VII., the following nominations have been prepared by the Nominating Committee, submitted to the Board of Directors at its October meeting, and are hereby published for the information of the members. For Director and President: Benjamin B. Thayer, District 0 For Directors and Vice-Presidents: Herbert C. Hoover, District 6 W. L. Saunders, District 0 For Directors : Reginald W. Brock, District 11 Charles W. Merrill, District 6 Albert R. Ledoux, District 0 Henry L. Smyth, District 1 D. C. Jackling, District 7 The Constitution further provides that " Any complete or partial ticket of nominees signed by any twenty-five Members or Associates of the Institute and transmitted to the Secretary by December 15 shall also be printed and circulated with the official ticket and over the names and with the recommendations of the nominators, together with an expression of opinion of the Board thereon if deemed expedient.

Jan 11, 1913

By S. L. Craig, C. Orr, H. G. Blocker

WITHIN recent years gas adsorption methods have been developed for measuring the surface area of finely divided materials and have become extremely valuable in research on the corrosion and the catalytic activity of metals. Rather elaborate apparatus is required, and a single determination is so time-consuming that these methods have not been utilized to the fullest extent; the methods are un-suited for most routine control work such as that encountered in powder metallurgical operations and in processes employing metal catalysts. These difficulties are largely eliminated, and surface area is reduced to a routine determination if the liquid-phase adsorption of a surface-active agent such as a fatty acid can be used. When the affinity of the fatty acid carboxyl group for the solid surface is greater than its affinity for the solvent, a unimolec-ular layer of orientated fatty acid molecules will be formed at the solid-liquid interface in a manner similar to that of a compressed fatty acid film on a water surface. The measurement of surface area is then reduced to a measurement of fatty acid adsorption. This propitious circumstance, first investigated by Harkins and Gans,¹ has been employed with somewhat inconclusive results by a number of investigators in evaluating the surface properties of metals, metal catalysts, and metal oxides. The specific surface area values for nickel and platinum catalysts, determined from the adsorption of a number of fatty acids from various solvents, were found by Smith and Fuzek² to agree with values calculated by the gas adsorption technique of Brunauer, Emmett, and Teller," he so-called BET technique. And recently Orr and Bankston4 have also reported good agreement between nitrogen gas and stearic acid adsorption results in the measurement of the surface areas of clay materials. On the other hand, Ries, Johnson, and Melik5 found only order-of-magnitude agreement between these two methods in studying supported, cobalt catalysts having specific surface areas as great as 420 sq m per g; the reason is partially attributable to the very porous nature of the materials. Greenhill,6 investigating the adsorption of long-chain, polar compounds in organic solvents on a number of metal powders, concluded that a uni-molecular layer of stearic acid was formed on exposure of the solid to the acid solution and that the presence of an oxide or another film did not alter this result. Furthermore, the adsorption process appeared to be the same whether or not the sample was degassed prior to exposure to the solution. Greenhill estimated the surface area of one of the powders he investigated from microscopic diameter measurements, and obtained a rough check with surface area evaluation. Russell and Cochran7 found moderate agreement for alumina surface area results by fatty acid and gas adsorption methods. In addition, they also found that the prolonged heating and evacuating pretreatments previously used by investigators were unnecessary. The present work, however, considerably extends these previous investigations, shows that fatty acid adsorption can be used to determine the surface area of a variety of metals and metal compounds, offers further confirmation of the correctness of gas adsorption methods, and presents a simplified technique for the determination of the metal surface area which is suitable for routine work. Experimental Technique Basically, the fatty acid adsorption method is quite simple. It consists of exposing a sample of the material of which the surface area is desired to a fatty acid solution of known concentration. By analysis of an aliquot of the solution, the concentration after adsorption has occurred may be determined. The difference between the initial quantity of acid in solution and the final quantity is that quantity of acid adsorbed by the sample. The specific surface area of the adsorbent material may be calculated from the quantity adsorbed and the weight of the sample. In agreement with the findings of others as outlined above, it was found entirely unnecessary to degas or pretreat the nonporous materials employed other than by drying them thoroughly. However, precaution was necessary so that the dried sample entered the fatty acid solution with little exposure to moisture. The effect of moisture on the interaction of stearic acid with finely divided materials has been thoroughly investigated by Hirst and Lancaster." They found the presence of water merely reduced the amount of acid adsorbed by powders such as TiO2, SiO2, Tic, and Sic. With reactive materials such as Cu, Cu2O, CuO, Zn, and ZnO, however, water was found to initiate chemical reaction. Only with ZnO was reaction observed when the solid and the solu-

Jan 1, 1953

By R. P. Aikman, F. G. Miller, J. M. Podgursky

In response to the growing demand for low-sulfur coking coal for iron-making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, (i.e., +28 mesh) at almost any desired specific gravity. However, in the case of fine coal (i.e., -28 mesh) neither of the two existing processes-froth flotation and hydrocycloning-in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this article is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods.

Jan 7, 1967

By Stuart McHugh, Douglas Keough

INTRODUCTION AND BACKGROUND Because of the potential for large reserves from increased production in the eastern Devonian shales, the Department of Energy (DOE), Morgantown Energy Technology Center (METC) selected these materials for the application and evaluation of existing and novel well stimulation techniques. One technique selected for further study was pulse tailoring, or tailored pulse loading, i.e., shaping the input borehole pressure history to produce a specific fracture pattern and to increase communication with the reservoir. The complexity and expense of in-situ mineback experiments prohibits direct evaluation of pulse tailoring in various geologic formations. An alternative approach used by SRI International consisted of evaluating fracture enhancement by computational simulations with supporting laboratory experiments and using data from field tests by other agencies to validate the computational model (McHugh and Keough, 1980). Laboratory experiments were conducted on core samples to determine fracture phenomenology and parameters and to verify material properties. The fracture parameters were obtained from posttest measurements of fracture distributions and correlation with stresses calculated by a wave propagation code. Model development was guided by these experiments and similar experiments in various materials performed by other agencies. The validity of the modeling, parameters, and scaling was evaluated by comparing fracture patterns from field tests with calculational simulations.

Jan 1, 1982

Florida State Geological Survey, Tallahassee, Fla Herman Gunter, State Geologist A list of publications will be sent upon request Citizens of the state may obtain publications available without cost, others may have them for postage, or they can be sent express collect Twenty Annual Reports have been issued from 1908 up to and including the 21st-22nd Annual Report (1931). Only three are now available; 4th Annual Report (1912), 15th (1924) and 18th (1927) Reports since 1921 contain statistics on mineral production. All reports contain papers on various subjects, many of which are still available separately, and are so indicated in the list of publications. Seven bulletins have also been issued, principally of interest to paleontologists Bulletin 7, The Pensacola terrace and associated beaches and bars in Florida (1931), is of more general interest Bulletins will be sent upon receipt of postage. Thirteen Press Bulletins, most of which are available, have also been issued, but are of minor interest

Jan 1, 1933

By ElRoy Nelson

WATER provides to many mineral industries functions similar to those performed by money in the economic system. Water is a medium of exchange. It is also required in chemical reaction for cooling, for transfer of minerals, and for cleaning. To a great extent, water is also a raw material in almost every industrial operation; it becomes a component of the finished product. In the Rocky Mountain region, water is treated with a great deal of respect. There has not been enough of it when needed. Long ago storage facilities were planned and devised to assure a supply during periods of shortages. This comes from the history of the region in irrigation and mineral processing. Within this region the shovel was always the most lethal weapon used in settling disputes over the use or misuse of water.

Jan 10, 1954

By N. Van Wingen

EFFECTIVE sand permeabilities can be ascertained from core analysis if the laboratory data are compensated to allow for the presence of connate or residual water. Such adjustments can be made by applying empirically derived correction factors. Effective sand permeabilities can be estimated also from analytical studies of field depth-pressure measurements. In one method the time rate of pressure build-up after a well is shut in from steady-state flow is required, and in the other the direct measurement of a steady-state rate of flow and the corresponding equilibrium pressure. The results of the investigation discussed in this paper demonstrate that these methods for determining mean effective sand permeabilities can be correlated.

Jan 1, 1942

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By P. E. Baker

The commercial neutron-gamma log measures the intensity of gamma-rays produced by the interaction of neutrons with nuclei in the formation and in the bore hole. This measurement gives information concerning the distribution of neutrons around the neutron source, and in particular gives information on porosity or fluid content. Another type of information is contained in the frequency or energy spectrum of the neutron capture gamma-rays. The capture gamma-rays of each element, in fact of each isotope, have only those energies characteristic of that isotope.'" The neutron capture gamma-ray spectrum, if obtainable, would permit the identification of the elements producing the spectrum. Such information would have considerable value in oilfield exploration work if it could be applied practically in well logging. Experiments have been carried out at the La Habra Laboratory of California Research Cop. to determine the feasibility of a method of well logging in which neutron capture gamma-ray spectra are measured down hole. In these experiments, spectra were obtained for artificial formations under simulated borehole conditions, using actual borehole geometry. This paper will describe the experimental apparatus and methods and will present the spectrum curves for several formations. THEORY Basic Formulas The neutron capture cross section of an element is a measure of its tendency to capture neutrons. The macroscopic cross section, or cross section per cubic centimeter, of a material composed of several elements is the sum of the cross sections of the nuclei making up 1 cc of the material. This is expressed in the equation SB = Sn1s2, ..........(1) where SB is the macroscopic cross section, s, is the cross section of a nucleus of type i, and ni is the number of nuclei of type i/cu cm. If N is the number of neutrons absorbed per second by the composite material, then the number captured by element j is Ni = N nisi/SB = N nisi/Si ni si ......(2) When the nucleus captures a neutron, a new nucleus is formed, which is usually in an excited state and falls to its ground or unexcited state by emitting one or more gamma-ray quanta.* The emission spectrum has been measured for many elements (see Table 1). The intensity of gamma-rays produced by an element is proportional to the number of neutrons captured per unit time by the element, which in turn depends on the capture cross section of that element and the capture cross sections of the other elements present which are competing with the first element for thermal neutrons. In a small sample of material the number of neutrons, N, captured per second is N = ?SB, ..........(3) where $ is the thermal neutron flux and SB is the macro-scopic cross section defined above. The number of neutrons captured by element j is N1 = ?ni si = N ni si/SB . ......(4) The number of gamma-ray quanta of energy, E, pro-duced per unit time by element, j, is I(E)=Nni si/SB P(E) .......(5) where P(E) is the emission probability of element, j, for this gamma-ray energy. Borehole Effects The capture gamma-ray spectra of many elements have been measured accurately in academic and government laboratories. These measurements are made on small samples, and from these measurements the emission spectra of the elements are obtained.

Jan 1, 1958

NOW continuing with the preparation of the moulds I say that it is necessary to give the greatest attention to the differences of the clays as well as to the differences of those things that you wish to mould; and to know that every concavity in the mould produces a convexity and every convexity a hollow following the shape of the original pattern that you have. The pattern should be a body of a harder mated than the thing [78] you wish to mould with and of a substance that is not swollen or disintegrated by moisture. Its archetype may be of marble, bronze, lead, or any other metal, or also of wood, wax, tallow, gypsum, sulphur, or other plaster compositions-in short, of whatever you may have or whatever succeeds best for you, depending on whether the works are large or small and easy or &cult to mould. If you wish to cast them in bronze, you must mould them with loam, covering them with it and then drying it. There are some things in which it is enough to form only one part, such as half- or bas-reliefs. These are easy if they have no undercuts. Some other patterns that are easily handled are formed in two halves, or in three or four pieces, if they are of a hard material. There are also moulds for large statues, which, if one desires to make them of bronze, are first made of wax according to the ordinary procedure. I have in mind to describe every one of these processes in their own place. There are like- wise some moulds that are difficult to make, like scenes on a plane to which figures in full relief are attached, or twisted ornaments or other detached things that cannot be withdrawn from the mould without break-

Jan 1, 1942

By F. Wald, A. J. Rosenberg

The general features of the constitution of the B-Pt system were determined using standard rnetal-lograph~c, thermoanalytic, and X-ray diffraction techniques. Three compound were found. Two of these, Pt3B and Pt,B, are formed by peritectic reactions at 523° and 890°C, respectively. The third, Pt3B,, is congruently melting with a flat maximum at 940°C but decomposes eutectoidally in to Pt,B ant1 boron nt - 600° to 650°C. THE low-temperature allomorph of boron (red, simple rhombohedra1 a boron) is of scientific and technological interest as an elemental semiconductor.' However, the studies of this material have been hampered by its reported instability above 1200"~ which precludes crystal growth from the melt (mp - 2200°C). Crystallization from platinum solutions has been suggested as an alternative crystal-growth technique, but has met with only limited success.' The technique depends upon the existence of a significant difference between the eutectic temperature and the transformation temperature of boron. In order to clarify the conditions for further crystal-growth experiments, we found it desirable to redetermine the main features of the B-Pt phase diagram since previous reports on the system1'5'6'7 are in marked disagreement. EXPERIMENTAL The experimental methods used were thermal analysis, metallography, X-ray analysis, and, to a lesser extent, measurements of microhardness. Most of the alloys were prepared from spectrograph-ically standardized boron obtained from Johnson-Matthey &Co., Ltd. (212 ppm impurities, exclusive of carbon and oxygen) and platinum powder obtained from F. Bishop & Co. (200 ppm impurities, mainly of other platinum group metals). Some alloys were also prepared with very high-purity, float-zone refined boron (99.9999 pct obtained from "Wacker Chemie" and extrahigh-purity platinum (99.999 pct) obtained from Johnson-Matthey & Co., Ltd. The reported results did not depend on the choices of these starting materials. Five-gram alloy specimens containing 10, 20, 25, 27.5, 30, 33.3, 34, 35, 37, 37.5, 38, 39, 40, 41, 42, 43, 45, 50, 55, 60, 70, and 80 at. pct B were made by melting the elements together in boron nitride crucibles using rf heating of a graphite susceptor, either in vacuum or under high-purity argon. All alloys were heated to at least 1800°C for -5 to 15 min. Most of the alloys did not wet the crucibles when the latter were outgassed by preheating under vacuum. In any event, no weight loss was detected after melting, and the nominal composition was assumed for all specimens. Thermal analysis on 2.5-g samples were carried out in boron-nitride crucibles under a vacuum of 5 x X torr. The apparatus was heated in a "Kan-thal A 1" wound furnace, which limited the maximum temperature to about 1100°C. The output of the indicator thermocouple was fed to a dc recorder with a 1-mv full-scale span and an adjustable zero. The apparatus was calibrated repeatedly, using the freezing points of high-purity aluminum, silver, and gold. The results justified the use of the NBS voltage vs temperature tables for Pt/Pt 10 pct Rh thermocouples. All thermal analyses were run at least twice and both the heating and cooling effects were recorded. Most of the alloys had a very strong tendency to supercool. However, the use of mechanical vibration permitted reproducibility within *5°C for all alloys, except in the region around 40 at. pct B. Only the cooling effects are plotted in Fig. 2, since they appear to be more reliable. For metallography, the alloys were cut with a diamond cutting wheel, cast in a polymethacrylate resin, ground and polished with diamond paste, and etched with dilute aqua regia, a common etch for platinum alloys. Both copper and molybdenum radiation were employed to obtain X-ray diffraction data using Debye-Scherrer cameras and a "Norelco" diffractometer Diffractometry with high scanning speeds (1 deg per min) using nickel filtered CuK, radiation was used to identify the main regions of the diagram. However, molybdenum radiation was used for the detection of boron, since the latter showed very strong absorption and fluorescence effects with CuK, radiation. RESULTS AND DISCUSSION Three intermediate compounds, corresponding to the compositions Pt3B, Pt2B, and Pt3B2, were found in the system. Fig. 1 reproduces their X-ray diffraction spectra, together with those of pure boron and pure platinum. As can be seen from the thermal-analysis data in Fig. 2, Pt3B and Pt2B are formed by

Jan 1, 1965

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By L. E. PORTNER

INCREASING military demands on the petroleum industry have brought into bold relief the crude-oil reserves now available to meet combined military and civilian demands, emphasizing the necessity for a greater efficiency in recovery from what has been discovered than ever before, particularly in light of the absence of new discoveries. This situation-and the fact that the industry, as well as members of the Government charged with governing oil production, desire to meet all crude-oil demands made of the industry with the least loss in tangible reserves through production practices-paves the way for increasing application of sound principles of production engineering and conservation.

Jan 1, 1944

By A. F. Baker, E. R. Palowitch, A. W. Deurbrouck

As air-pollution regulations become increasingly more stringent, increased significance is being placed on the amount of sulfur present in coals used for steam generation. These regulations are aimed at minimizing the pollution of the atmosphere with noxious gases such as the sulfur oxides that are formed and emitted when coal is burned. Two meet these future requirements, a definite need exists to reduce the sulfur content of some of the coals used for steam generation. Reducing pyritic sulfur involves liberating the pyrite from the coal and then removing it. The specific gravity of pyrite is high (5.0) compared to that of coal (about 1.2, mineral-free), and standard coal-washing devices, such as wet concentrating tables, will efficiently remove pyrite particles larger than about 100 mesh. Particles below this size will be entrained in the table water and will be carried into the clean coal product. Techniques such as froth flotation are of little benefit for pyrite reduction because the flotation characteristics of pyrite are similar to those of coal.

Jan 6, 1966