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By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.' Recent work' indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken's 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. 'V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By S. Leber

Pole figures and pole distributions were used for the quantitative detevinination of the preferred orientations in swaged tungsten rods and the effect of subsequent wire drawing on the texture. In the swaged rod, the preferred orientation could best be described as a pseudo (111-112) [110] cylindrical texture. A secondary component was assigned the indices (110) [001]. Further reduction by swaging retained these cylindrical textures. Wire drawing caused lattice rotations about the wire axis, converting the cylindrical texture into a normal fiber texture. The conversion was initiated and proceeded lnost rapidly in the center of the wire. The (110) /001] component was converted into a (110) fiber texture by wire drawing. The effective rotations were about axes contained in the lransverse plane. The preferred orientation associated with tungsten wire usually has been assumed to consist of a (110) fiber texture. This implies rotational randomness around the wire axis. Leber1 has shown that rotation about the wire axis may be restricted resulting in a preferred orientation designated as a cylindrical texture. Specific crystal planes tended to remain aligned parallel to the wire surface. This texture seemed to be the result of the swaging operation used in the intermediate stages of fabrication. Bhandary and cullity2 detected similar textures in swaged iron wires. Peck and Thomas3 suggested that the preferential alignment of crystal planes parallel to the wire surface was the result of tangential flow, characteristic of swaging. Wire drawing, following swaging, twisted the crystals about axes parallel to the wire axis, converting the cylindrical texture into a normal fiber texture.4 In this investigation, quantitative techniques were used to more accurately characterize the cylindrical texture and to study its conversion into a normal fiber texture. PROCEDURE The material investigated was lamp-quality tungsten. Three ingots were rod-rolled and swaged to 112 mils diameter, and were then drawn to 10-mil wire. Samples were obtained after each drawing pass. (110) and (200) pole figures were obtained from samples prepared as shown in Fig. 1. To form the sample shown in Fig. l(a), l-in. lengths of wire were glued side by side to form a l-in. square. The composite was ground and electropolished to form a diametral reference surface. For certain specific tests, samples were prepared as shown in Fig. l(b). This composite was made from 10-mil-thick strips prepared by grinding on parallel longitudinal planes. The polished reference surface in this case was, in essence, the wire surface. The two forms of samples [~igs. l(a) and l(b)] were related by a 90-deg rotation around the wire axis. Because of ease in preparation, most data was obtained from the diametral samples. The X-ray data were obtained using a Siemen's pole-figure goniometer. These data were not corrected for absorption or defocusing effects, since only the angular locations of the intensity maxima were of interest. Regions of the pole figure more than 80 deg from the center were not investigated. Partial monochromatization was achieved by the use of unfiltered copper radiation and a krypton-filled proportional counter. No evidence of spurious white radiation effects5 could be detected. Therefore, more elaborate X-ray techniques were not required. Intensity levels were chosen to show all pertinent details of the orientation distributions. The reference plane for the pole figures was the diametral section. The orthogonal reference directions, shown in Fig. 1, were the wire axis, the radial axis per-

Jan 1, 1965

By W. C. Hagel, H. J. Beattie

Phases present at 2200° and 1500°F (1204° and 816°C) were identified in sixty wrought developmental austenitic alloys possessing wide compositional variations. The bases were iron-, cobalt-, and nickel-rich as well as a base with equal parts of each. There are only two structure types previously not found in similar alloys, viz .-the Co3 W and the Fe3Al types. A molybdenum-rich monocarbide decorates dislocations with unusual clarity. Other results provide correlations between alloy composition and phas e precipitation. Grouping intermetal -lic phases into three general classes : I) geometrically close-packed, 2) topologically close-packed, and 3) bcc derivatives, the nickel base prefers the first, the iron base the second, and the cobalt base the third—each base tending to shun the other two classes. Thus, a crystal-chemistry effect previously noted by Laves and Wallbaum can he expanded for these Group VIII elemental bases. There appear to he no quaternary or higher -order structure types requiring more than three atomic species. AFTER studying aging reactions in many diverse commercial austenitic alloys1-4 as a function of detailed time-temperature variations in heat treatment, it became apparent that matrix composition influenced structure types and morphologies to a large extent. These tendencies were related4 to a crystal-chemistry effect uncovered by Laves and Wallbaum.5,6 We have now directed our efforts to exploration of the whole ternary field, covering the standard base elements—iron, cobalt. and nickel— with 10 to 20 pct Cr and moderate amounts, up to 10 pct, of the usual alloy additions. Solutioning and aging treatments were held constant with major emphasis on X-ray identification of microconstituents. The possible existence of exceptions to the Laves-Wallbaum effect, or any new phases, was sought. Phases appearing in austenitic alloys can be classified as geometrically close-packed (gcp), octahedral or nonoctahedral interstitial compounds, topologically close-packed (tcp), semicarbides, and bcc derivatives. Crystal structures of the first four classifications can be visualized as a dense packing of semirigid spheres of different sizes, while the bcc derivatives represent a less efficient packing of spheres. The Laves-Wallbaum effect involves the gcp and tcp phases. Gcp phases possess both tetrahedral and large octahedral interstices; examples are Ni3Ti(n), NiSAl(y'), Co3W(E), and other ordered AB3 compounds where B atoms are smaller than A. Their precipitation is primarily intragranular, presumably coherent with an austenitic matrix, and a chief source of strengthening. Most octahedral interstitial compounds (e.g., CbC, Tic, TiN, Mo2C) have a gcp lattice of large metal atoms which accommodate small carbon or nitrogen atoms in the octahedral interstices. The compound Ti2SC, previously designated Y phase or T phase, can, with some reservation due to its partial co-valency, be placed in this category.7 The nonoctahedral interstitials (e.g., M7C3, Fe3C) represent close-packings of spheres in structures that provide larger triangular-prism interstices for carbon, since the octahedral interstices formed by chromium and iron atoms are too small. Tcp phases possess only tetrahedral interstices; examples are Laves (Fe2Ti, Fe2Cb, Fe2W...AB2), p(Fe7MO6, Co7W8.... A8B7), and (FeCr, Co2Cr3)

Jan 1, 1965

By E. F. Sumner, C. K. Eilerts

A partial differential equation was developed and programmed to compute the cumulation and flow of the liquid phase of a gas-condensate fluid. It was found that such cumulation near the wellbore may attain saturations permitting liquid flow within periods of the order of 1 day. The radius at which this saturation obtains advances toward the external reservoir boundary with continued recovery, although it may move only 2 to 5 percent of that distance during the productive life of the well. This relatively high saturation can cause a serious dimunition in delivery capacity. The pressure dilferential required for flow of gas through a formation with such saturation may be as much as three times greater than the corresponding differential in a formation where saturation is less than 2 percent. Because of the radial geometry, total reservoir pressure differential required for flow with a zone of relatively high liquid saturation about the well was indicated to be two to three times greater than without the saturation. INTRODUCTION A computing program developed by the authors 1 to integrate the partial differential equation for transient radial flow of gas-condensate fluids required a prevalued function, W(Po) = kD(p0)/M(p0)z0(Po).......(1) related to cumulation of condensate in pores of the reservoir as pressure declines. Methods were available for relating mobility to saturation, saturation to liquid-vapor volume ratio, liquid-vapor volume ratio to pressure and, hence, mobility to pressure to obtain W(pD). However, certain assumptions had to be made in advance of program execution concerning movement of the liquid phase and change in radial distribution of liquid saturation as recovery progressed. Because reservoir fluid mobility and related pressure gradients are markedly dependent on liquid saturation, it was desirable to eliminate the necessity for these assumptions and in this respect improve the reliability of a result obtained by integration. Experimental research was begun to determine the relationship of variables that control the reservoir flow of low liquid-vapor ratio fluids. With the porous medium partly saturated, permeability to a two-phase flowing fluid could not be measured because the viscosity was unknown. Viscosity could not be measured without knowing permeability of the liquid-containing medium; but mobility, the ratio of permeability to viscosity, was measurable. This property, and liquid-vapor volume ratio of the flowing phases, have values determined by nature of the fluid and porous medium and, in addition, were found to be pressure, velocity and saturation dependent. A program developed by Kniazeff and Naville 2 for computing multicom-ponent, two-phase flow used polynomials to represent saturation dependence of permeabilities for gas and for liquid phases, and an effluent viscosity constant under reservoir conditions. The authors developed a program based on a partial differential equation of similar mass balance origin but designed to represent distribution of an unlimited number of components between gas and liquid phases utilizing the experimental information available as to variable dependence. Attention was given to liquid-vapor volume ratio of the flowing phases, a property which is essential as a liquid saturation boundary condition. A program for computing implicitly saturation increase at uniform intervals along the drainage radius was combined with an existing program for calculating pressures, and the two were used alternately in an iterative solution for both saturations and pressures. The function W(pD) needed for calculating pressures was replaced by the ratio of mobility to compressibility factor. BASIC EQUATIONS The partial differential equation for calculating

By M. C. Fuerstenau, A. M. Gaudin

A homogeneous suspension is viewed by X-rays. The radiation density seen, affords a measure of the extra absorption due to the solids contained. This radiation density, at a predetermined depth, varies with time. The chart of this relationship gives the desired determination. s it is frequently necessary to know the distribu-rt tion of particle sizes in various products used in industrial applications, a number of means have been devised for these determinations. Some of them include direct microscopic measurement, screening of product, extraction of samples from a settling slurry, air and liquid elutriation, adsorption of gases and liquids, and light absorption. The absorption of light as a means for particle size analysis has been known and employed for some time. X-ray absorption has not received the attention that light has enjoyed primarily because of the complex and costly instrumentation involved with X-rays. In 1954, Brown and Skrebowskil suggested the use of X-rays for this type of determination but did not supplement their suggestion with experiment. In 1958, the authors conducted size analysis experiments on suspensions of quartz with the Trans-viewer: an X-ray unit specifically adapted for sedimentation research, and Rossa conducted experiments in a similar manner in 1959 with a stable gamma emitter, AmZ4l, on suspensions of uranium oxide. To illustrate the applicability of X-ray absorption for analyzing particle size distributions, an essentially mono-energetic and well collimated X-ray beam was used as a source. The beam was made mono-energetic by placing a zirconium filter before the counting window together with feeding the pulses from the proportional counter into a reverter, a device capable of discriminating against pulses of various heights. The sketch in Fig. 1 shows the collimation arrangement in more detail. As shown, the X-ray beam was collimated by inserting a 3/8-in. ID pipe into one of the ports of the X-ray tube and further by two small steel plates with slits 3/32-in. wide and 1/2-in. long placed in front of the window of the Geiger-Mueller (G-M) tube. One of the plates was located 1/2 in. and the other 2 1/2 in. from the window of the counter; both plates were contained in an aluminum holder mounted on the box containing the G-M tube. This type and degree of collimation should eliminate any intensity due to scattered radiation; the transmitted intensity would then be solely a functior. of the absorption by the suspension at that level. Experimentally, homogeneous suspensions of finely ground quartz were prepared, Daxad (a sulfo-nated compound made from wood) was added as dis-persant, and the transmitted X-ray intensity measured as a function of time at a fixed depth in the suspension. In more detail, the experimental procedure involved the following: 1) measuring the transmitted X-ray intensity through the Daxad solution at a predetermined position or settling depth in the absence of solids, 2) placing a known amount of dry solids into the vessel and agitating thoroughly, 3) measuring the transmitted X-ray intensity at time zero (i.e., immediately upon cessation of stirring), and 4) measuring the transmitted X-ray intensity as a function of time (a 10-sec counting interval being chosen and counting being started 5 sec before the desired time). Since a linear relationship exists between percentage solid in a slurry and the logarithm of transmitted intensity for a homogeneous material, the cumu-

Jan 1, 1961

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer' and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations. Geology Composition and Morphology Diatomaceous silica qualifies as a. mineral of organic origin in much the same way that aragonite and collophane do. The silica of the fossilized diatom skeleton closely resembles opal or hydrous silica in composition (SiO2 • nH2O) .4, 12, 203 The silica is of acute biological significance, not only for the cell wall component, but also for the basic life process.45, 51 Without silica, cell development ceases .31 In addition to bound water, varying between 3.5 and 8%, the siliceous skeleton may also contain, in solid solution, or as part of the Si02 complex, small amounts of associated inorganic components-alumina, principally-and lesser amounts of iron, 46, 49, 55 alkaline earths, alkali metals, and other minor constituents.59, 63, 67 Boron is reported to be an essential element for diatom growth .52, 58 Since diatomaceous silica is not pure hydrous silica but contains other intimately associated elements, there is good reason to consider it a distinct type or variety.4 Associated with the diatomaceous silica, and integrated as part of the diatomite, may be variable amounts of organic matter, soluble salts, and particles of rock-forming minerals that were syngenetically deposited or precipitated with the diatom frustules. Sand, clay, carbonate, and volcanic ash are typical common contaminants. Other contaminating minerals may be present, such as feldspar, mica, amphiboles, pyroxenes, rutile, zircon-the result of weathering, then transporting, and subsequent redeposition of surrounding land masses. Commercial diatomite may also contain fragments and particles of

Jan 1, 1983

By Robert Keeney

THE electric smelting of manganese ore and the production of ferro- manganese did not exist as an industry, in the United States or elsewhere, previous to the outbreak of war in 1914. Ferromanganese had been produced, electrically, during times of high prices by two companies at Niagara Falls and by several European companies, but the production. was spasmodic, and none was electrically produced when ferromanganese sold at from $35 to $40 per ton. Thus the electric smelting of manganese ore must be considered as a development caused by the high prices prevailing during the years 1916, 1917 and 1918, and the necessity of smelting domestic ore in order to fill the ferromanganese requirements of the steel industry of the United States, which increased from 189,088 tons in 1914 to 356,356 tons in 1918. The electric furnace is well adapted to smelting domestic-ore because it can be located in small units near the source of ore supply. In 1918, the ferromanganese production of the United States was 333,027 tons, of which about 7 per cent., or 23,000 tons, was produced in the electric furnace. The electric furnace not only assisted materially in the development of a domestic-ore supply but made a considerable saving of coke, as it requires about 1,4 tons of bituminous or lignite coal per ton of ferromanganese compared with a blast-furnace consumption of 2.9 tons of coke per ton of ferromanganese. Some of the plants in the United States that smelted manganese ore in the electric furnace during the war and in 1920 are listed in Tabled. From early in 1919 to about February, 1920, little ferromanganese was produced in the electric furnace. During this period the price of ferro-manganese (78 to 82 per cent. manganese) was about $100 per ton. During the first half of 1920, several plants resumed operation when the, price of. ferromanganese (76 to 80 per cent. grade) gradually increased to $200 per ton, delivered.

Jan 2, 1921

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By Thomas L. Kesler

Essentially all of the barite produced in Georgia has come from the Carters-ville district in the northwest part of the state. The earliest recorded shipment of ore, 60 tons, was made in 1894.' With the exception of the four-year period 1931 to 1934, the separate yearly output has been recorded and published since 1915, whereas the total yearly output of the United States has been published since 1880. The separately recorded production of Georgia (Cartersville) through 1947 is 2,232,544 short tons valued at $14,900,746,2 but unpublished data on the period 1931 to 1934, plus the estimated unrecorded output prior to 1915, make the actual total about 2,400,000 short tons. This is about 21 pct of the total production of the United States, which, through 1947, is 11,328,440 short tons valued at $71,683,386.2 The barite-producing part of the Cartersville district is relatively small, having from north to south a length of 4.5 miles, and a width of 2 miles. This small area, containing 35 barite mines, is the source of practically all of the barite produced in the state. The area is hilly, and has a total relief of 500 ft. The west-flowing Etowah River crosses the middle of the area, and is an unfailing source of water for operations on properties near its course. Opencut mining is carried on during the entire year, but is hampered by rain in the winter and early spring. Three railroads, two U.S. highways, and a network of graded roads provide access to and within the district, as well as excellent shipping facilities for ore and supplies. In addition to the barite, the district contains deposits of manganese, brown iron, ocher, umber, and specular hematite. Geologic Setting The area containing the barite deposits is underlain by Lower Cambrian rocks and their weathered residua. These rocks are grouped in three formations; in ascending order, these are the Weisner, the Shady, and the Rome. The Weisner formation consists mainly of finely micaceous metashale containing many random beds of quartzite, a few beds of conglomerate and metasiltstone, and beds of crystalline limestone that is apparently scarce. The formation is more than 1000 ft thick, and the base is not exposed. On account of their resistance to weathering, the rocks of the Weisner formation have sustained the higher elevations and therefore crop out on the ridges that characterize the area. Nearly all of these ridges are underlain by asymmetric anticlinal folds, and conversely the intervening valleys are underlain by synclinal folds. A diagrammatic section, showing typical mode of exposure of the Weisner rocks and their relation to overlying formations, in the limb of a fold, is shown in Fig 1. The Shady formation here consists of a lithologically distinctive series of variably siliceous specular hematite beds and thin beds of dolomite, which in places contain abundant fossils. In the zone of weathering, the dolomite has been leached and most of the hematite hydrated to ocherous and umber-ous clays, hut bedding planes in these weathered materials are commonly well preserved with or without distortion effected by slumping. This preservation of structure during weathering is lacking in the residuum that rests on the Rome dolomite, which is described below. The maximum thickness of the

Jan 1, 1950

By Oscar Johnson

The industry has been canvassed for information on methods of handling grinding steel at milling plants, an important subject overlooked in most descriptive articles on milling plant arrangements. The data collected are offered in this paper as a guide to designers and planners who have loading and storage problems to solve. WITH capacities of milling plants expanding from a few hundred tons per day to many thousand, replenishment of grinding media is an important phase of mill operation. Information on this aspect of milling procedure, solicited from several mining companies, is summarized here. At International Nickel's Copper Cliff concentrator the normally strenuous job of changing rods is considerably simplified by the use of the Garrow rod charging machine, Fig. 1. The overhead crane, Fig. 2, brings a bundle of rods, weighing four to a ton, to the loading platform of the machine, positioned in front of the mill. The rods roll one by one down the slight incline of the platform onto a conveyor which sends them into the mill. A modified version of the Garrow machine, Fig. 3, is used at the Federal mill of St. Joseph Lead Co. An overhead crane places the portable steel structure in position in front of the discharge end of any one of the five 9x12-ft rod mills. It then raises a bundle of about twenty 3-in. rods to the discharge platform of the charging machine. The rods are 11 ft 7 in. long and weigh about 278 lb. By tripping a lever the operator allows one rod at a time to roll onto the inclined rollers. A slight push by the operator sends the rod smoothly into the mill. The Union Miniére du Haut Katanga rod charging machine, Fig. 4, is mounted on a pair of wheels at the forward end with swiveling castors at the back for steering it to position for use or storage. Wheels are equipped with locking brakes to maintain the machine in position while it delivers rods to the mill. The device is made in two parts. The first consists of the base, which carries the supporting wheels, grooved rollers, and drive. The other part serves as the rod deck, which can carry up to six 3-in. x 12-ft rods. A short boom built integral with the base reaches through the mill trunnion and delivers the rods into the mill barrel. Three grooved guide rollers ,are provided to receive the rods from the sloping charging deck. One rod at a time is fed to the rollers and thus delivered into the mill. Two of the rollers are driven by 11/2-hp motor through a V-belt drive. The third roller is driven off the first by a single V belt in a groove below the rod groove and on the same center line. Rods are delivered to the charger by an overhead crane in bundles of three to six as needed. The power is supplied by cables plugged into power outlets, suitably located near the rod mill discharge end. The Oliver Iron Mining Co. uses a rod charger, Fig. 5, suspended from a monorail by cables. It is constructed .of structural steel and has two decks, each capable of carrying five rods of 4-in. maximum diameter. The rods ride in grooved free-turning rollers. Legs extending down from the mill end of the mechanism act as supports when the unit is ex-

Jan 1, 1955

By H. S. Price, D. A. T. Donohue

The system of equations describing displacement of a hydrocarbon liquid by a hydrocarbon vapor in a porous medium where mass transfer takes place between the phases is solved numerically for a variety of gas injection processes. Even though the method of solution is quite general, only systems with three hydrocarbon components are considered. Computer simulations of displacement processes wherein mass transfer between phases is both considered and neglected are compared, and it is shown that neglecting mass transfer can give pessimistic displacement efficiencies. INTRODUCTION The role of the gas displacement process in the recovery of petroleum has been subjected to a series of detailed analyses; as a result, a number of predictive models have been published in the literature. However, because of major simplifying assumptions, most of these models do not completely represent the physical system. As a result, the effect of making the simplifying assumptions is unknown. Therefore, a complete representation of this process — one without major simplifying assumptions —should lead to a fuller understanding of the process, and perhaps to methods of improving it. The general method of developing a model for two-phase fluid flow in a porous medium is to solve simultaneously the continuity equation, the energy equations and the equation-of-state for each phase under the prescribed initial and boundary conditions. For an isothermal system, the energy equations reduce to the momentum equation. Darcy's law. However, since natural gas is the vapor state of the reservoir liquid, interphase mass transfer may take place with concomitant changes in both the intensive and extensive thermodynamic properties of each phase. It is this phenomenon that has often been omitted in previous mathematical models. An additional relation, then, which accounts for mass transfer between the phases, must be included with the other equations to specify a complete model. Completely formulating the equations to be solved is not a difficult task1 but obtaining their solution has been intractable up to now. Availability of large-memory, high-speed digital computers now makes an attack on this formidable problem possible. This paper presents a preliminary study of the problem. Since this investigation is intended to be exploratory, it is restricted to the linear, horizontal, isothermal, two-phase viscous flow of oil and gas in an oil reservoir. In the early development of predictive models of this process, the reservoir system was considered as a unit and various forms of the material balance equation were proposed.2-4 Pressure and saturation gradients were then added in the Buckley-Leverett model.5 The Buckley-Leverett formulation considered the fluids to be incompressible; thus, the mathematical model reduces to a steady-state system. In the 1950's, studies incorporating numerical techniques were being published.6-9 These mathematical models differed in the efficiency of finite difference techniques, the inclusion or exclusion of capillarity or the number of space dimensions considered. To solve these nonlinear, partial differential equations, each phase was considered to be homogeneous with time; therefore, mass transfer between phases was neglected. The effect of mass transfer on the gas displacement process was first reported by Attra. 10 He simulated the one-dimension flow system by a series of cells in each of which the fluids were equilibrated during a time step. In addition, the pressure throughout the system during each time step was predetermined and constant-phase velocities were calculated according to the Buckley-Leverett incompressible fluid flow model. Welge et al.11 developed a model for the displacement of oil by an enriched gas where composition is considered to be a dependent variable. Fluid

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

By C. A. Hartnagel

The production of petroleum in New York in 1940, totaling 4,999,000 bbl., was only slightly under the amount produced in each of the previous three years. The year 1940 started auspiciously with a posted price on Jan. I of $2.75 a barrel. Four price reductions, beginning in May, resulted in August in a low of $1.85 a barrel, after which two increases brought the year's closing price to $2.15 a barrel. The favorable crude price at the beginning of the year stimulated an increased drilling program, especially in the water-flooding districts. In the Allegany County region, which accounts for about two-thirds of the state's oil production, 886 wells, including water-intake wells, were drilled; 200 more than in the preceding Year. During the closing months of the Year there was a marked decline in the number of wells drilled. The unfavorable position in which the industry found itself before midsummer was due largely to the loss of export markets for its high-grade lubricants, constituting approximately 25 per cent of its business. As a result of this situation, runs to refineries were curtailed as much as 30 Per cent at the middle of the Year. Improvement in market conditions toward the end of the Year found the stocks of available crude at an almost record low. Deep DRILLING with the gradual exhaustion of some of the important natural and flood-oil-produc-ing areas of the Allegany and Bradford pools, overproduction will not be a serious problem in the future. The possibility of finding new territory or deeper producing sands has been further lessened by the drilling of additional deep wells for gas in and about the present oil fields. Many of these wells drilled to the Oriskany sand-stone were over 4000 ft. deep and have tested the entire thickness of the Devonian formation, the upper 2000 ft. of which contain all the important oil-producing strata in the state. Water-flooding It is thus evident that the problem of the New york oil producers is not one of find-ing new supplies but of obtaining as much 6 oil as possible from the old developed fields that during the 60 years of their life have 1 produced I 3o,ooo,ooo bbl. of oil. Although a few floods were in operation before I9I9, when the production of oil by flooding was 1 made legal, the output for that year amounted to only 85I,000 bbl. From 1919 I on there has been an almost constant increase, which during the past four years has averaged well above 5,000,000 bbl. annually. During the last 22 years, which constitutes the period of important flooding operations, 651337,000 bbl. of oil have been produced in the state. Careful estimates indicate that between one-third and one-half of the oil fields are being flooded or are already watered out. Some of the flooded and watered-out areas include territory with unusually thick sands, which were highly productive during the early history of the fields. From a recent study of operations in the New York oil fields, it is estimated that about 65,ooo,oo bbl. of oil

Jan 1, 1941

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

By E. H. Edwards, J. Washburn, E. R. Parker

The mechanism of strain hardening was discussed in connection with some recent observations on the stress-induced motion of dislocation boundaries and on the simple shear deformation of zinc, cadmium, and copper crystals. THE nature of work hardening accompanying plastic deformation of metals has long been the subject of speculation. As early as 1925, Becker' suggested a thermodynamic process to explain slip based on the statistical probability for the occurrence of local glide steps. The theory that plastic glide was due to the presence of lattice defects known as dislocations was first introduced in 1934 by Taylor: and Orowan, and Polanyi.4 Taylor presented a rather complete analysis of the behavior and interaction of dislocations. He assumed a certain type of stress field to be associated with a single dislocation, and postulated that work hardening would result from plastic flow in two ways. First, dislocations following one another across a slip plane might encounter a barrier which would impede their movement, thereby gradually diminishing and eventually stopping plastic flow on that plane. The second mechanism involved the concept of dislocations traveling in opposite directions on nearby planes attracting one another to form a meta-stable lattice. The interaction of dislocations in such an array was shown to be large enough to require an increase in stress before plastic flow would continue. Kochendorfer5,6 extended the concept of work hardening involving a back stress due to an accumulation of like dislocations on a slip plane. He suggested that the formation of a new dislocation is hindered by those dislocations already present. The hardening resulting from the interaction of newly forming dislocations with bound dislocations was designated as "formative hardening," and indicated to be the only type of hardening necessarily connected with the slip process. In another detailed picture of work hardening, Mott and Nabarro7 assumed that sufficient dislocations are primarily present in the crystal as a consequence of growth irregularities (mosaic structure) to initiate slip. Work hardening resulted from the interaction of migrating dislocations with localized internal stresses produced during deformation. More recently, however, Mott8 as modified his treatment to include the generation of dislocations at Frank-Read sources and he accounts for the hardening by the formation of sessile dislocations. It has been widely accepted that metals of hexagonal structure, usually possessing only one set of glide planes, exhibit mechanical behavior markedly different from those having cubic structures. However, the differences in behavior of the two classes may be less fundamental than suggested. Rohm and Kochendorfer9 have shown that a single crystal of aluminum subjected to approximately simple shear gives the type of stress-strain curve associated with the hexagonal metals. Similar behavior has been demonstrated for gold and silver crystals by Andrade and Henderson.'" Thus when glide in cubic metals is restricted to one plane, the strain hardening characteristics closely resemble those of the hexagonal metals. It would appear, therefore, that an investigation of some of the strain hardening properties of single crystals sheared in simple glide might provide a more complete understanding of the phenomenon of work hardening. This report relates a number of recent observations made on single crystals of copper, zinc, and cadmium tested in simple shear. In addition, pertinent observations of effects accompanying stress-induced movement of dislocation boundaries are reported. Experimental Procedure and Results Details of the production and advantages of the type of single-crystal shear specimen employed for the following tests have been presented in a previous publication.n The method of testing makes

Jan 1, 1954

By S. C. Sun

With the aid of emulsifiers, intense high-frequency sound waves are capable of emulsifying any collector in water. The data show also that ultrasonically emulsified collectors are more effective in floating minerals than the nonemulsified collectors. THE use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and OstrawskyV escribed the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanaka3 employed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets In the other. The dispersed liquld is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses, 5a, B proposed for the formation of emulsions, the Bancroft's adsorbed film or double interfacial tension theory is widely accepted. Bancroft 7, 8 deduced that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids. This film has two interfacial tensions, one with the water and the other with the oil, which are not necessarily equal. The difference in interfacial tension between the two surfaces of the film is chiefly responsible for forming different types of emulsions. For example, if the interfacial tension between water and film is less than that between oil and film, the film will become convex on the water side, thereby tending to form an oil-in-water emulsion. On the other hand, if the interfacial tension between water and film is greater than that between oil and film, the film will become concave on the water side, thereby tending to make a water-in-oil emulsion. In line with this theory, emulsifying agents soluble in water have the tendency to form oil-in-water emulsions, while those soluble in oil form emulsions of the reverse type. Apparatus and Experimental Procedure: The ultrasonic apparatus shown in Fig. 1 consisted of a hypersonic generator (A), Brush Development Co. model Bu-204; a hypersonic transducer bowl (B) whose resonant frequency is 400 kc per sec; and a round-bottomed glass tube (C) of 2.2 cm ID and 21 cm in length. The acoustical output power of the hypersonic transducer bowl was standardized with a Hewlett Packard vacuum tube voltmeter, model 41 0B, across the hypersonic generator output. The glass tube, containing the materials to be emulsified, was placed 1 cm above the central surface of the transducer bowl, which was filled with water as shown in Fig. 2. Ultrasonic emulsification was performed in three steps, although a one-step method has been used: 1) emulsifying the predetermined amounts of col-

Jan 1, 1956

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By R. L. Hadley, G. Derge

The amounts of oxygen in liquid iron-titanium alloys up to 50 pct Ti were measured and the oxide phases in equilibrium with these alloys were determined by using TiO² crucibles. A minimum of about 0.003 pct 0 occurs at less than 1 pct Ti. The various liquid and solid oxide phases can be arranged on a ternary isotherm. THREE characteristics of titanium contribute to the interesting aspects of its reaction with oxygen in liquid iron: 1—It forms a number of stable oxides. 2—All oxides have large negative free energies of formation. 3—The pure metal exhibits high solubility for oxygen. In addition, the use of titanium as a stabilizing and strengthening element in alloys suggests a need for investigation of its reactions in amounts greater than those normally required for deoxidation. These higher compositions are also of interest because they occur during the addition of ferroalloys and produce deoxidation products before dilution is achieved. Titanium Deoxidation in the Literature While the use of titanium as an alloying element and deoxidizer has been common for several decades, the first detailed study of its deoxidizing characteristics was carried out by Wentrup and Hieber' in 1939. These authors determined the extent of deoxidation possible with titanium and identified, by microscopic examination, the products formed. They found that titanium in excess of 0.2 pct did not reduce the oxygen content of iron below 0.004 pct at 1600°C. They identified the spinel FeO-TiO² at low titanium concentrations and Ti2O³ in melts containing more than 0.2 pct Ti. A portion of the area surveyed by Wentrup and Hieber has been investigated recently by Evans and Sloman² using X-ray diffraction for inclusion identification. They concurred in general with the findings of Wentrup and Hieber, but reported the existence of Ti³O5 as a deoxidation product in the range near 0.1 pct Ti. Comstock, Urban, and Cohen³ discussed the deoxidation of iron with titanium, correlating the data of Wentrup and Hieber with free-energy data for the titanium oxides. Scatter at high titanium values was considered attributable either to the formation of an oxide exhibiting high solubility in liquid iron or to the entrainment of solid oxide particles leading to high apparent solubility. Chipman' has calculated the deoxidation curves for titanium based on free-energy data for titanium oxides. These calculations (Fig. 1) and those of Comstock, Urban, and Cohen involve assumptions as to the activity coefficients of oxygen and titanium in liquid iron, since such data have not been determined. Investigation of the deoxidizing characteristics of chromium" and vanadium0 have shown that these elements decrease the activity coefficient of oxygen in liquid iron, leading to a tendency toward relatively high oxygen values and experimental scatter in highly alloyed melts. Experimental This investigation involved two major objectives: 1—determination of the composition of the oxide phases in equilibrium with liquid Fe-Ti alloys, and 2—establishing the pattern of oxygen solubility in liquid Fe-Ti alloys at titanium concentrations in excess of that required for attainment of minimum oxygen content. Raw Materials Ingot iron was used having the following composition: 0.02 pct C, 0.017 pct Mn, 0.01 pct Si, 0.02 pct S, 0.006 pct P, and 0.03 pct 0. The titanium used

Jan 1, 1956

By R. E. Barnes

An overall view of the perlite industry is concisely presented. The geology, mining, milling, processing, and applications of perlite, as well as the present status of the perlite industry are treated. Perlite, in strict petrological usage, describes a specific variety of volcanic glass in which strain, incident to cooling, yielded a concentric structure of fracturing which may be visible either to the naked eye or under a microscope. In commercial usage, the term perlite includes any naturally occurring acidic glass of volcanic origin that will expand when heated to a suitable temperature. The name perlite is a derivation of perlstein which originally defined "certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."1 While perlite has been known to geologists for many years, it was not until 1941, while investigating perlite for use in enamel, that an assayer in Superior, Ariz., noted the unusual expansion characteristics of the ore. Further investigations were delayed until following World War II when many small plants were built and experimentation in the treatment and uses of perlite began. The Perlite Inst. was organized in 1949 to promote the development of the new industry, establish commercial standards through research, and to explore new uses and markets. The Institute, located in New York, represents some 50 producers in the U.S., Canada, Australia, England, France, Germany, Greece, Japan, Mexico, and New Zealand. In 1949, 71,l002 short tons of crude perlite were produced, sold or used by U. S. producers, and this figure increased to 325,0003 short tons by 1959. Such a rate of increase indicates the rapid and continuing growth of the perlite industry. GEOLOGY Perlite ore in its crude form has been found in seven of the mountainous western states, since un-devitrified siliceous volcanic rocks are limited to this section of the U. S. Commercially operated perlite deposits are normally of Eocene and Oli-gocene age.4 These deposits are often several hundred feet thick and may extend over hundreds of acres. In 1959, 13 companies in six states produced crude perlite, although the output in New Mexico comprised 79 pct of the total domestic crude output. Other states in order of their production were: Nevada, Arizona, California, Colorado, and Utah.5 Foreign deposits of perlite which are either producing or under exploration are Australia, Canada, Greece, Hungary,6 Iceland, Ireland, Japan, Mexico, New Zealand, and Sardinia. The ore may exhibit a variety of characteristics depending partially on its water content and eruption history and may range through many shades from black to white. While these characteristics may vary slightly among deposits, perlite ore from a particular source is normally quite uniform. Available chemical analyses of perlites from a large sampling of domestic deposits were recently assembled by the Technical Committee of Perlite Institute and are presented in Table I. While the ranges given do not apply to a particular perlite, they are an indication of the chemical analysis which may be expected from any presently commercially operated deposit. The specific gravity of the perlite ore ranges between 2.2 and 2.4, and its bulk density when crushed and sized is 75 to 90 Ib per cu ft. MINING AND MILLING Perlite ore is quarried from open pits by conventional power equipment, although blasting has been occasionally employed. The rock is then stock-piled until needed. While the milling of perlite may seem a simple process compared to that required for basic metals, or even other nonmetals, the need for accurate control of particle size becomes extremely important in further processing. The first step in this operation is the primary crusher, which is normally a jaw crusher. Following crushing, the material is dried, if necessary, in a rotary dryer and conveyed to a secondary grinder which may be a rod mill, hammer-mill, or cone crusher. However, the crushing characteristics of the perlite, caused by incipient cooling fractures, requires it be removed from the grinding operation once it is reduced to the required size so as to prevent overgrinding. Following the grinding operations, various size screens are used to separate the ore according to particle sizes required for particular uses. Most plants use two or more stages of crushing with perhaps four stages of screening.

Jan 1, 1961