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By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17' of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns'10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By I. W. Alcorn

THE cost of drilling in the past few years of proration and ever decreasing allowables has received increasing thought and study. It seems to parallel the strides made with respect to pumping problems in 1932 and 1933. Low profit margins stimulate the search for economies. Any discussion of slim-hole drilling involves a multitude of abstract values, and the problem can be attacked only by a study of records and rational thinking. In a measure, traditional methods must be studied with a questioning attitude. The words "slim hole" may be somewhat misleading, as the term is entirely relative. For that reason I wish to define it as used in this discussion. On the Gulf Coast, I would define a normal hole as one in which 10 3/4-in. surface casing has been set and below which a 9 7/8-in. hole is dug. With this as a datum, holes of larger diameter below surface would be called "large holes," with 12 1/4 in. as the "extra large" class and holes of smaller diameter classed in the slim-hole range, 6 1/4 in. representing about the minimum size. The optimum size has not been definitely determined, but the preference is for a program that would call for setting 8 5/8-in. surface casing and digging a 7 3/4-in. hole. Different sections of the country might very properly deviate from this practice because of differences in depth, formations, regulations, or other factors. This paper will be confined to a discussion of the drilling of exploratory wells, as the drilling of this class of wells is quite a different problem from that of drilling a proven field, although many of the same considerations apply in both cases, as will be apparent. Although for many years shallow slim-hole and core-test holes of small diameter had been dug, it was not, I believe, until the fall of 1937 that serious consideration was given to its application in drilling wells 7000 ft., 8000 ft. and 9000 ft. deep on the Gulf Coast. This does not mean that nearly all such wells drilled on the Gulf Coast now are of the slim-hole variety, but only that efforts have been aimed in that direction with very encouraging results and there has been a very definite trend to reduce the size of holes, a trend that probably will continue. As to exploration policy, there appear to be two distinct and opposite views. The one usually followed in the past was more or less designed to "shoot the works" on one well. Generally on the Gulf Coast, the depth at which production might be obtained is limited by the drilling equipment and economics. With this thought in mind, wildcat wells are often planned with the idea of carrying the depth to 10,000 ft., or even 15,000 ft. All of the possible hazards are anticipated and the general drilling and casing programs are so predicated. Such wells contemplate the drilling of large-diameter holes; the setting of at least one protective string of casing and an extensive coring policy, all of which finally adds up to an expensive well. As opposed to this general policy is the slim hole. This, on the Gulf Coast, recognizes that new discoveries represent gam-

Jan 1, 1941

By C. H. Gorski

A method for preparing titanium tetrachloride is described which consists of reducing rutile with coke and chlorinating the reduced product at 200° to 500°C. The crude distillate is purified by treatment with copper powder and distillation. Recoveries, exceeding 90 pct of the titanium in the rutile, were obtained. IN recent years considerable interest in metallic titanium has been aroused because of its outstanding physical and chemical properties. The present commercial processes for preparing titanium are modifications of the Kroll1 process and consist essentially of the reduction of titanium tetrachloride with magnesium in an inert atmosphere to produce metallic titanium with magnesium chloride as a byproduct. At present,' commercial titanium tetrachloride costs $0.32 a pound, which makes the price of the included titanium $1.28 a pound. As the titanium tetrachloride must be purified further before processing into metal, its ultimate cost obviously will be higher. Consequently, one of the prime requisites for the production of lower cost titanium metal is a source of low-cost titanium tetrachloride. Recently, Knickerbocker, Gorski, Kenworthy, and Starliper3 escribed a method for preparing titanium tetrachloride from low-grade Arkansas rutile by smelting the rutile with pyrite and coke to form a titanium matte and then chlorinating the titanium matte to prepare a crude titanium tetrachloride. This process had several inherent advantages. Low-grade rutile concentrates were utilized, the chlorination temperature was relatively low (approximately 200°C), and the reaction was strongly exothermic. However, this process had several disadvantages, chief of them being the rather low recoveries of titanium tetrachloride (65 to 81 pct) and the difficulty in purifying the crude titanium tetrachloride obtained. Because of the high-titanium and low-iron con- tents of rutile as compared to ilmenite, rutile should be of greater potential value as a source of titanium tetrachloride than ilmenite. Rutile, however, is not chlorinated directly in commercial practice, because reaction temperatures above 700 °C are required, at which point chlorine attacks most of the common materials of construction. The process now in use consists of converting the titanium in rutile to the cyanonitride by high-temperature reduction in an electric furnace, and then chlorinating this compound. The disadvantages of this process are the difficulty of producing the cyanonitride, the use of high-grade rutile concentrates in the charge, and the presence of several percent of silicon tetrachloride in the finished product. It would be of considerable interest to develop a new process for the preparation of titanium tetrachloride from rutile by chlorination at 200" to 500°C. Process Development Several investigators'-' have studied the reduction of titanium dioxide with carbon in an effort to prepare titanium monoxide. Invariably, the titanium monoxide formed in this manner was not pure, as it contained titanium carbide and one or more of the lower oxides of titanium. As these lower oxides of titanium are more reactive chemically than rutile, and as it is known that titanium carbide may be chlorinated readily, a study was made of the chlorination of carbon-reduced rutile. A sample of rutile concentrates from Hot Spring County, Ark., containing 76.19 pct TiO,, 5.65 pct Fe2O3, 4.18 pct SiO2, and 2.88 pct Al2O3, was used for this investigation. The experimental procedure consisted of making an intimate mixture of —100-mesh rutile and petroleum coke, adding water and molasses as a binder to foi-m a paste, charging into a graphite crucible that was covered, except for a vent to allow the

Jan 1, 1952

By A. J. Teplitz, J. K. Rodgers, E. M. Pohoriles

This note is presented in order to call attention to a newly developed laboratory apparatus that appears to have interesting possibilities for the study of lost circulation of the pressure-parting type, for a more realistic evaluation of sealing materials for this type of loss, and for investigation of other aspects of hydraulic fracturing. A study of lost circulation, conducted jointly by operating divisions of the Gulf Oil Corp. and the Gulf Research & Development Co., has been in progress for the past few years. Earlier phases of the study dealt with mechanical factors contributing to loss of returns in laminar type sediments.' One aspect of this type of loss which has been widely discussed in the literature and elsewhere concerns the geometry of the fractures into which such losses occur. This subject is not merely a philosophical one, but has an important bearing on procedures for combating lost circulation difficulties and on other well operations. The further course of the collaborative studies previously mentioned has produced some information on this subject which, though limited in amount, is believed to be significant. In several typical cases of lost circulation in laminated shale and sand formations, the wells have been surveyed with instruments2,3 capable of detecting the points of loss with considerable accuracy. These wells were located in the Gulf Coast of Texas and Louisiana, in the Texas Panhandle, and in the Rocky Mountain area. In each of these instances the loss was shown to be occurring at some distance removed from the bottom of the hole and sharply confined to a very narrow interval, less than 1 ft in thickness. It is rather difficult to imagine that fractures of a vertical nature' would be of the limited extent indicated by the surveys in these wells. Furthermore, the high rates of loss at relatively low pressure differentials observed in some of these instances together with the narrow intervals involved would appear to require the radial flow pattern which would be associated with a more or less horizontal fracture plane. In view of the foregoing observations and records of successful squeeze cementing operations, in attempting to construct a laboratory apparatus For simulating pressure induced lost circulation, it was decided that the design should be based on a horizontal type of fracture. It was realized that5,6 Vhe production of horizontal fractures in a formation with non-penetrating fluid requires some mechanism for transmitting vertical components of the hydraulic forces to the plane of parting. This was accomplished, as will be evident in the description of the apparatus that follows, by providing recesses in the wall of the borehole which are believed to be representative of wellbore configuration found in Gulf Coast wells. The possible influence of such borehole irregularities on both pressure fracturing and the treatment of lost circulation appears to have been neglected in many studies of these subjects. It is believed that the present apparatus, incorporating features that take into account some of the factors mentioned, will provide means of gaining a further understanding of pressure induced fracturing and possibly for more realistically evaluating the numerous sealing agents, particularly the non-time-setting materials employed in treating the pressure-parting type of loss. DESCRIPTION OF APPARATUS The test cell used in the laboratory investigations is shown in Fig. 1. A schematic diagram of the entire system is shown in Fig. 2.

Jan 1, 1956

By G. S. Hume

During the war years the drilling activity in Canada has been steadily increasing and still further increase is expected in 1945. The production of oil, which in the past has come largely from the Turner Valley field in Alberta, shows a decline since 1942, the peak year. New discoveries made in 1944, however, give promise of replacing the decrease from Turner Valley where the crude-oil production in 1944 was nearly 1,800,000 bbl. less than in 1942, but with an increase of 145,000 bbl. in natural gasoline, a product of great value to the war effort. A very considerable part of the decline in Alberta has been offset by new production of more than a million barrels in 1944 from the Norman Wells field, in the Mackenzie River area of the Northwest Territories. It should not be forgotten, however, that this is largely due to the Canol development, a war project, the future of which is dependent on many factors not connected with an ordinary commercial operation. The year 1944 has been the best in new discoveries in Alberta for all time. The discovery of a new deep field at Jumping-pound, 20 miles west of Calgary, with the hopc of a type of product similar to that of Turner Valley is the culmination of many years of effort to interpret the subsurface structures in relation to the complicated surface foothills faulting and folding. In this case the subsurface structure on the Paleozoic limestone was inferred from geological investigations but precisely defined by seismograph. In addition to Jumpingpound the discovery of oil of 34.5 gravity at a depth of less than 5000 ft, in the Devonian of the Plains at Princess, 125 miles east of Calgary, is of great significance since this is the first substantial production from the Devonian in Alberta, although previously some oil had been obtained at two places from the Devonian in the foothills. The effect of this discovery is already apparent in the number of wells now drilling to the Devonian in the southern Plains. In southern Alberta a new producing area has been found in a Lower Cretaceous sand at Barnwell, a few miles west of Taber. Also, at Conrad, 20 miles southeast of Taber, an important new discovery has been made at a depth of about 3000 ft. in a sand in Jurassic shales, in a strali-graphic trap on the northeast flank of the Sweetgrass arch. In northeast Central Alberta an important extension has been found in the Lloydminster area, where only a few wells have so far been drilled. A new well 3 1/2 miles south of the previous producers found a coarser sand at the productive horizon and as a result will have an increased daily yield. At Blackfoot, 9 miles west of Lloydrninster, a new producing area in the Lower Cretaceous may have been discovered at a depth of 2004 ft. At the end of 1944 the well was being tested. Forty-four unsuccessful wildcat wells were drilled in Alberta in 1944. The decline of Turner Valley, the major producing field, was anticipated at the beginning of the war and in an effort to offset this and encourage new development the Dominion Government put into force tax concessions and other measures that,

Jan 1, 1945

By Philip R. Strand

Vermiculite is the name used for those micaceous minerals with a ferromagnesian aluminum silicate composition and the unique property of exfoliating to a low density material when heated. Commercially, the exfoliated products are also called vermiculite, or more exactly, expanded vermiculite. In its exfoliated state, vermiculite serves many markets, chief among them construction, agriculture, horticulture, and general industry. Composition and Properties Vermiculite, in a natural state, has the characteristic mica habit, splits readily into thin laminae, flexible but inelastic. In a mineralogical sense, vermiculite is a hydrated silicate with no exact chemical composition. The structural formula for a macroscopic, trioctahedral vermiculite may be written: [ ] The structure of vermiculite is basically that of a talc, and it could be regarded as a trioctahedral member of the smectite group. Macroscopically, vermiculite displays the prominent monoclinic crystal faces that are commonly marked by lines at 60° and 120°. Hardness varies from 1.5 to 2.8 or more; specific gravities are between 2.1 and 2.8; color is amber, bronze, brown, dark green, or black. When heated quickly to an elevated tempera¬ture, vermiculite expands by exfoliating at right angles to the cleavage, into wormlike pieces (the name vermiculite is derived from the Latin `vermiculare,' to breed worms). This characteristic of expansion, the basis for commercial use of the mineral, is the result of the mechanical separation of the layers by the rapid conversion of contained water to steam. The increase in bulk volume of commercial grades is 8 to 12 times, but individual flakes may expand as much as 30 times. All expansion occurs at right angles to the basal cleavage. Vermiculite may also be expanded by a number of chemical processes such as soaking in hydrogen peroxide, weak acids, and other electrolytes. There is a color change during expansion that is dependent upon the composition of the vermiculite and furnace atmospheres. Heating in an oxidizing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. The exfoliation of the vermiculite crystal results in large pores being formed between groups of platelets. Thus exfoliation can make available a large increase in void volume without significantly changing the surface area of the platelets. This characteristic is important in the chemical carrier applications of vermiculite. Although there has been much research on the chemical and structural composition of vermiculite, an exact formula and composition cannot be described. This is to be expected since vermiculite derives from a number of different mineral sources. As has been proposed, vermiculite is not a single mineral species, but families of related minerals. Additionally, commercial interest in the end product has resulted in the name vermiculite being applied to the very voluminous, bloated products from calcination of baueritized (bleached) phlogopite. This has also resulted in many names for the specific vermiculite found in a particular deposit. All of this difficulty arises from the nature of its crystal chemistry. Consequently, vermiculite is now thought of as several related variable mineral series rather than a group of related species. The vermiculites have a common silica tetrahedral sheet structure with separating ions. It is now generally agreed that vermiculites must also be regarded as true clay minerals. The properties of the mineral, such as cation exchange capacity, organic complexing ability, and vari-

Jan 1, 1975

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.', ' Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds' of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies' of the slags, slag weights, the metal particle theory,' ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat' is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By E. E. Wahlstrom

The Harold D. Roberts tunnel, in Summit and Park Counties, Colorado, is a concrete-lined pressure tunnel finished to a circular cross section of 10.25 ft diam. The tunnel is 23.3 miles long and is designed to transport water for domestic use by the City and County of Denver from reservoir storage at Dillon to a tributary of the South Platte River at Grant. The tunnel passes beneath the Continental Divide at the crest of the Front Range and intersects rocks of diverse types and origins and geologic structures of extreme complexity. Geologic investigations preceded and were continued during construction and contributed materially to the safe and economical advance of the tunnel headings. Geological data obtained and evaluated during construction include plans and sections on a scale of 1 in. to 50 ft, rock temperatures at 2000-ft intervals, records of progress related to geology, records of ground-water conditions, summaries of the use of steel and timber supports, and summaries of grouting operations. Adverse conditions required use of steel and timber supports for 71.74% of the total length of the tunnel. Most supported sections reached a condition of equilibrium within a few hours to a few months after being excavated, and the concrete lining serves chiefly to provide an additional safety factor and to provide necessary hydraulic characteristics to the tunnel. Efforts to attain a maximum rate of advance of the tunnel headings necessitated use of more steel and timber supports than would have been required in a less accelerated tunneling operation. This report summarizes geologic investigations prior to and during construction of the Harold D. Roberts tunnel in Summit and Park Counties, Colorado (Fig. 1) and analyzes the tunneling operation as it is related to the various kinds of geologic conditions encountered in the tunnel. The tunnel is concrete lined to a circular cross section of 10.25 ft and is designed to transport 788 sec ft from reservoir storage at Dillon 23.3 miles along a dog-leg course passing under the Continental Divide to outlet and control works at Grant, Colo. The primary purpose of the tunnel is to augment the domestic water supply of the City and County of Denver, but plans include provisions for power generation at the outlet portal at a future date. Location of the tunnel was made after extensive preliminary geologic and engineering investigations by the Board of Water Commissioners of the City and County of Denver, and the U.S. Bureau of Reclamation. In 1946 the Board of Water Commissioners started tunnel driving on a limited scale from the east (outlet) portal and by 1955 had completed 9986 ft of tunnel. An urgent need for additional sources of water supply required acceleration of the tunneling operation, and, in 1955, Tipton and Kalmbach Inc. of Denver were assigned the responsibility of reviewing the project and preparing plans and specifications for the tunnel and appurtenant features. Additional geologic studies were made, and the geology of several possible alternate tunnel lines were compared before determining that the tunnel should be driven along the course previously adopted by the Board of Water Commissioners. On July 12, 1956, a contract for construction was awarded to Blue River Constructors Inc., a combine

Jan 1, 1962

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By C. W. Phillips, D. N. Frey

A commercial Ti-Fe-Cr alloy, Ti-150, exhibits a martensitic transformation on cooling and two nucleation and growth reactions, one above and one below the Mg-Mf region, on isothermal holding below the single-phase ß temperature range. The reactions were followed by metallographic, X-ray diffraction, and microhardness methods. THE rapidly expanding engineering application of titanium and its alloys makes increasingly urgent an adequate knowledge of the effect of heat treatment on this material. The work herein reported is an attempt to determine certain aspects of the behavior of a commercially available alloy, Ti-150, during heat treatment. The alloy, with a nominal composition of 2.7 pct Cr, 1.3 pct Fe, 0.25 pct 0, 0.02 pct N, and 0.02 pct C, was received in the as-rolled condition as a 3/4 in. round. Slugs 0.11 to 0.12 in. thick were cut under a coolant using a silicon carbide wheel. Preliminary work established that the alloy consists of two phases, a (hexagonal close-packed) and /3 (body-centered cubic), at temperatures below 1750" to 1775"F, and of only /3 phase at higher temperatures. The slugs were heated for 1 hr in air at 1800°F to form a single-phase /3 matrix, then transferred to molten tin (1250° to 1650°F) or lead (1150°F and below) for isothermal holding. Holding temperatures ranged from 700° to 1650°F, times from 0.001 to 23 hr. The treated slugs were then sectioned, one part for metallographic examination and diamond pyramid hardness, the other, after deep etching to remove the high oxygen surface,' for comparative lattice parameter determination and X-ray phase identification. Hardness measurements were taken on the lightly etched surfaces of the metallographic specimens; a 1000 g load on a 136° diamond pyramid was used. Five impressions on each sample were made and the average of the hardness calculated. The use of microhardness measurements to follow the course of an isothermal transformation reaction is undesirable because of the possibility of wide differences in microconstituent hardness.' They were used in this case, however, because of the small amount of material available. At the higher transformation temperatures, where the above-mentioned objection was apparent, the readings were proportioned to correspond to the estimated ratio of transformed and untransformed constituents present. At lower temperatures, resulting in much finer microconstituents, the microhardness measurements were more uniform. The standard deviation of the mean of five impressions calculated from these latter values was 4.2 DPH. Employing 2a limits (probability 0.95) the experimental error of the hardness measurements averages was 8.4 DPH. The etchant used was composed of one part glyc-erol and one part 48 pct hydrofluoric acid." Of a number of etches tried, this one appeared most satisfactory. All micrographs were taken at 500X magnification and with oblique lighting to permit easier identification of the acicular structure resulting from rapid cooling. No advantage was gained by using polarized light for metallographic examination. Phase identification and lattice parameter measurements were made with a North American Philips high angle spectrometer in conjunction with a recording potentiometer. Considerable difficulty was encountered with some of the lattice parameter measurements because of the extreme broadness of the few diffraction lines obtained from samples consisting mainly of strained, untempered, quenched structures.

Jan 1, 1953

By C. E. Violet, R. J. Borg, E. M. Howard

The miscibility gap in the Au-Ni system has been determined by Mossbauer spectroscopy, with used as a probe. The phase boundaries were determined from the compositional dependence of both the isomer shift and Curie temperature. X-ray diffraction measurements were also used to confirm the Mossbauer results. 1 HE purpose of this research is to demonstrate the application of Mbssbauer spectroscopy to the determination of phase boundaries and to redetermine the miscibility gap by an independent and novel technique. The techniques evolved in this study are readily applicable to other polyphase systems and are generally as quick and accurate as the more conventional methods, e.g., metallography, X-ray diffraction, thermal analysis, and so forth. To be sure, not all polyphase systems will lend themselves favorably to Mijssbauer investigations, but this is a problem met in the use of conventional methods as well. The Mbssbauer spectrum responds to a different set of physical parameters, and consequently provides an entirely independent method of analysis. It is especially useful if the system has either a ferromagnetic or an antiferromagnetic transition. The Au-Ni system was selected because alloys containing more than -60 at. pct Ni become magnetically ordered at low temperatures; also the miscibility gap is quite well established (see Ref. 7 for a compilation of pertinent references, also Fig. 11, and thus provides a reliable test of this novel procedure. As Fe is the most commonly used Mijssbauer isotope, there exists a wealth of information concerning its behavior in iron-containing alloys and compounds. However, as yet there have been relatively few experiments using it as a probe to investigate nonferrous systems. By choosing a nonferrous alloy system, we are able to demonstrate that its use is not restricted to systems containing iron as one of the major constituents. Wertheim and ~ernick' have used the same method to investigate Cu-Ni, and demonstrated that one can obtain a systematic variation in the isomer shift and magnetic hyperfine field. However, we believe this to be the first time these techniques have been used to establish phase boundaries. Two hyperfine interactions were measured and used to determine the phase boundaries, viz., the magnetic hyperfine splitting and the isomer shift which in this alloy system are both strong functions of composition. Calibration curves were established based upon single-phase solid solutions obtained by quenching from temperatures well above the maximum of the miscibility gap, see Fig. 1. Solid solutions containing 25, 50, 65, 75, 85, 92, and 96 pct Ni as well as pure nickel were used in the calibration procedure. Fig. 2 shows the Curie temperature, TC, and the isomer shift, v,, as determined from the Mbssbauer spectra, and variation in lattice parameter as determined by X-ray diffraction, as functions of composition. The compositions of the two-phase systems quenched from temperatures within the miscibility gap are obtained by comparing their respective values of TC and v0 with the calibration data. I) EXPERIMENTAL Mbssbauer sources were made by fusing the component metals in a tungsten arc melter, which has a water-cooled copper hearth. Both nickel and gold were 99.999 pct pure, and the melting was done in an atmosphere of purified argon. The alloys were rolled, diced,

Jan 1, 1969

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By C. K. Eilerts, J. D. Ham

Laboratory research has been conducted to evaluate the characteristic effects of condensate saturation on the mobility of gas in typical reservoir rocks. A pump with two pistons provided phases in equilibrium at controlled flow rates and constant liquid-vapor volume ratios. Core samples were tested in a holder that permitted sealing steady-state phases in the pore spaces under flow test pressures for weighing with sufficient precision to give an accurate measure of the attained saturations. Parameters of the study were pressure, apparent velocity, flowing liquid-vapor volume ratio, fluid composition, core material and length-to-diameter ratio. Tests were conducted at 515 and 1,515 psia to determine the effect of pressure on the mobility-saturation relationship. Influence of the apparent velocities 0.30, 0.15 and 0.07 cm/sec and of five liquid-vapor volume ratios from 0.0001 to 0.01 was determined at 515 psia The principal fluid system was nitrogen and and separator liquid from a Gulf Coast condensate, but the effect of a condensate of different viscosity was also determined. The significance of a possible concentration of liquid near the outlet end of the test cores was investigated. Core materials included a consolidated sandstone and a low-permeability limestone. Relative mobility and liquid-vapor volume ratio relationships are concluded to be dependent on pressure, saturation and, to a lesser extent, on velocity. For each porous medium and fluid there is a minimum saturation essential to two-phase flow, and high velocities of flow have only limited effect on saturations in this range. INTRODUCTION It is now recognized that knowledge of the availability of a reservoir gas — the period that gas may be recovered from a reservoir at a given rate — is as important as the estimate of gas in place. When reservoir conditions are such that pressure decline owing to production will result in retrograde condensation, liquid saturation can increase in the structure around the production well in a way that may restrict flow capacity, and hence future availability. l Based on a numerical solution of transient radial flow of single-phase gas-condensate fluids, 2 a program for computing the accumulation of condensate in a reservoir and the effect of this condensate on deliverability has been developed. During this development a need evolved for data that described the influence of pressure, velocity of flow and condensed liquid on mobility as recovery progressed. This paper presents the results of experimental investigation to obtain insight into the mobility relationship at reservoir pressures of gas-condensate fluids. A core holder for flow tests at reservoir pressure was developed to weigh the core and its fluid contents under pressure to determine saturation. A specially constructed pump was used to drive a two-phase fluid through the core until a steady state prevailed. The core was used as a differential device, and properties measured were intensive rather than extensive. APPARATUS Fig. 1 shows a schematic representation of the major pieces of equipment used in the mobility determination. The weighable core holder is connected to a two-piston, constant-displacement pump. Attainment of steady-state flow is indicated by stability of the flow differential read from the high-pressure manometer. WEIGHABLE CORE HOLDER An important part of the data needed was the mobility-saturation relationship. This required that mobilities and saturations be measured at pressures, flow velocities and liquid-vapor volume ratios characteristic of condensate reservoirs.

By H. C. Chao, W. F. Hosford, L. H. Van Vlack

The negative "plastic Poisson's ratio" suggested in earlier studies of Mus deformation is analyzed, and the results are verified experimentally with NaCl crystals. In the early stages of deformation where the primary {110}(110) slip predominates, compression along. the [001] direction produces contraction along the lateral [011] direction plus a compensating expansion along. the [100] direction. With additional strain, the primary slip is supplemented by secondary {111}(110) slip so that the above contraction diminishes and a more typical deformation appears. THE shape change of bee and fee crystals deformed by compression or tension along [011] has been analyzed in some detail and shown to be responsible for the development of peculiar microstructures in [011] fiber textured polycrystals of these metals.1'3 This paper concerns the unusual shape change accompanying [011] compression of NaCl crystals. It is the direct outgrowth of an earlier investigation of the deformation of manganese sulfide inclusions in steel.3,4 In that investigation, cylindrical specimens of steel containing small oriented crystals of MnS were prepared by powder metallurgy and plastically compressed. The flow of the inclusions was determined relative to that of the steel by sectioning the composite and measuring the length-to-width ratio L/W of the inclusion and diameter-to-height D/H ratio of the steel cylinder on the plane of section. These L/W ratios, normalized by dividing by the initial LO/WO ratio of the inclusion, were compared with the normalized D/H ratio of the steel cylinder. Of particular interest here are the deformation characteristics of an inclusion oriented with [Oil] parallel to the compression axis. When measurements were made on sections parallel to the (100) plane of the inclusion, the L/IV ratios were only slightly in excess of unity, indicating a high apparent hardness of the [011] criented inclusion. However, measurements on a (011) plane of section resulted in L/W ratios which were much larger, Fig. 1. These observations prompted an analysis of the strains resulting from slip in an MnS crystal compressed along [011.]. CRYSTALLOGRAPHIC ANALYSIS Manganese sulfide has the NaCl crystal structure, and the predominant slip system is {110}(110). A secondary system, {111}(110), has also been reported.= {110}(110) Slip. When a crystal is subject to a uni-axial compressive stress 011 along [011], four slip systems, (101)[101.], (101)[101.], (110)[i10], and (110) [ 110], will be equally stressed with a shear stress t = 0.2 011 while the other two {110}( 110) systems will be unstressed. The normal strain En along any reference axis n resulting from slip is given by Schmid's law: en = S COS ?in COS in ?i 111 where ?in and +in are the angles between n and the i slip direction and n and the i slip plane normal, respectively, and where ?i is the shear strain on the i slip system, For the four active slip systems above, the cos ?in cos +in terms are all equal when the reference axes are the [011] compressive axis, [011] and [ 100]. Eq. [I.] therefore reduces to en - cos ?n cos +ny [2] where y =S?i for all slip systems. Substituting the appropriate angles, Eon = 0.25? 110 eon - 0.25y110 [3] €100 = -0.50y 110 The interesting feature of Eqs. [3] is that they predict that the strains in the [011] and [011] directions, resulting from {110}(110) slip, are equal and of the same sign. Thus when a crystal is compressed along [011], it will contract along the lateral [oil] direction

Jan 1, 1967

By H. R. Stahi

THE ore of the Southeast Missouri lead district consists essentially of galena in dolomitic limestone. The galena usually is in a very finely disseminated condition. The experience of recent years in the concentrating plants of the St. Joseph Lead Co. has shown that dry crushing carried to a point where about 90 per cent of the ore passes a 14-mesh screen liberates the larger portion of the galena, and minimizes further necessary reduction in rod or ball mills. Concentration practice has attempted to carry size reduction to a point where economic unlocking of the galena is obtained, without causing undue sliming of the very friable galena. While 60 per cent of the tonnage of the district is treated by the flotation process, only 40 per cent of the total concentrates is produced by that means, as efforts have always been made to keep the grade and tonnage of flotation feed as low as possible. The milling practice of the district for some years has recognized the generally accepted idea of better selective grinding in rod mills as compared with ball mills, with the attendant decrease in production of fines. The function of rod and ball mills in the various concentrating plants is the grinding of table middlings and coarse tailings that carry lead values too high to be discarded. The simplified flowsheet in Fig. I illustrates the place of grinding mills in the circuit. The arrangement of classifiers, tables and mills constitutes a closed circuit within somewhat flexible limits. In 1937 experiments were conducted in replacing the ball charge in a 6 by 4-ft. ball mill with rods 2 in. in diameter and 51 in. long. This step was taken with some hesitancy, as it was easy to picture a mass of tangled and crossed rods. However, no difficulties developed, and after a short trial period, six more ball mills were converted to rod mills. These mills are of the spur gear and pinion, belt-driven type, using in most cases a 75-hp. motor and having a 9 1/2 -in. open trunnion discharge. As ball mills, they carried a charge of 16,000 to 20,000 lb. of balls, 2 in. in original size. The feed to the mills was dewatered by dewatering wheels and introduced at 70 to 75 per cent solids, with a single scoop feeder. One change in mill design was found advisable when rods were introduced. The existing end liners had an outward flare of 3 ½ in. in 12 in. These were replaced by linings having vertical interior faces, in order to prevent undue end travel of the rods. This change gave an effective working length of 5 2 ¾ in. inside the mill. No alterations were made in the shell liners, which are of the smooth type, made of manganese steel 2 in. in original thickness. The rods at present in use are 51 in. long and 1 3/4in. in diameter. The composition has been varied at times; at present they contain 0.70 per cent carbon and 0.70 per cent manganese. Some breakage and etching occurs as the rods become small, but this is considered preferable to using softer rods, which may kink and cause tangling of the charge. The mill charges are renovated occasionally, broken pieces being removed and the charge brought up

Jan 1, 1945

By L. O. Howard

R. HATCH, Garfield, Utah.-The object of the meeting, I believe, is to determine the proper chemical composition to insure long wear of a ball in a mill, This might also apply to rods. I feel that there is only one way of determining accurately the wearing qualities of balls in mills, and that is by actually wearing out 400 or 500 tons of different kinds of balls. Two things add to the wearing qualities of a ball: (1) the tenacity, with which the particular particles of iron or steel are cemented together; (2) the individual hardness of each particle. My experience is that a ball that has a Brinell of 550 to 650 will give comparatively long life. There is considerable difference of opinion as to the best steel and iron alloys necessary to produce a satisfactory grinding ball. Some favor chrome, some manganese and some nickel. Personally, I believe cast iron alloyed with chrome makes the best ball for small sizes; for large sizes (3 1/2 in. and up) steel alloyed with manganese is best. L. 0. HOWARD, Pullman, Wash.-How would this method apply to lining? A. KissocK, New York, N. Y.-I do not subscribe to that exactly. As I am connected with the Climax Molybdenum Co. you would hardly expect me to. We have been much interested in trying to work out this grinding-ball problem and have spent a great deal of thought and effort on it. As we are associated with the American Metal Co. and have a number of properties of our own, we are in position to try our ideas on ourselves first. We have tried different compositions, but have not done anything very remarkable with them yet, except that we have been able to say that the combination of chrome and molybdenum has given the best wearing ball. Mr. Hatch feels that iron is the best medium for grinding, but since toughness as well as hardness is a factor in wearability we feel that a well made steel is better for this purpose. Another difficulty with cast, or chilled, iron is lack of uniformity from day to day or from heat to heat and the impossibility of producing balls free from blow or shrinkage holes which materially affect their life. If cast iron is made hard it becomes brittle and lacks stretch or toughness. This prevents its use in the larger sizes, as breakage is a serious handicap to efficiency. We have tried hard and brittle balls and softer but very tough balls and have proved that maximum hardness, with sufficient toughness to prevent breakage, is the most important factor in resistance of a steel to abrasion. It is well known that chromium is one of the best hardening agencies for either iron or steel, and molybdenum is recognized as an element capable of introducing toughness. In other words, the proper combination of chromium and molybdenum permits unusual hardness with still sufficient toughness to stand up under severest impact. It is yet too early to give any actual mill results of this new combination and though we are proving our ideas at our own properties we have to depend on others to help us make the data more general and more worth while and would like to get some tests

Jan 1, 1928

By Charles W. Chesterman

Perlite is a glassy volcanic rock which will, upon rapid controlled heating, expand or "pop" into a frothy material of low bulk density, valued as a lightweight aggregate. The term perlite also is applied to the expanded product. The chemical composition of perlite ranges from that of rhyolite to that of andesite; the water content ranges from 2 to 5%. Most perlite is pale gray, but some is black, brown, or even green. Inclusions in perlite are common and include phenocrysts of quartz, feldspar, biotite, and hornblende, and miscellaneous rock fragments. Occurrences of perlite are restricted to areas of Tertiary and Quaternary volcanic rocks. Perlite occurs as flows associated with thick accumulations of pyroclastic debris and other flow rocks, as dikes, sills, domes, and as selvages of intrusive bodies of volcanic rock. Individual flows of perlite range in thickness from a few feet to as much as 100 ft and commonly cover several square miles. Dikes and sills of perlite generally are small, but domes generally are substantial in size and may be as much as several miles in diameter. Most perlite deposits are large enough and topographically situated so as to lend themselves to low-cost open pit mining methods. Conventional equipment is employed in the mining of perlite. Although milling procedures may appear to be simple, care is exercised in order to produce a carefully sized product and to minimize the production of excessive quantities of fine materials, which have limited use and are considered as waste. Perlite is processed, or "popped," in one of two basic types of furnaces: horizontal rotary or vertical stationary. Both types of furnaces include product collection and dust control systems. Many commercial deposits of perlite are known to occur throughout the world, and although no exact estimate of reserves is available, there appears to be an adequate supply to meet current and future worldwide requirements. End Uses The uses of expanded perlite are many and varied and are based primarily upon its physical and chemical properties. Because of its (1) low bulk density, which generally ranges between 2 and 20 lb per cu ft; (2) low thermal conductivity "K" factor (Btu per hr per sq ft per OF per in, of thickness), which ranges between 0.267 for loosely packed perlite (bulk density of 4.48 lb per cu ft) to 1.25 for perlite gypsum plaster; (3) high resistance to fire; and (4) low sound transmission, expanded perlite is used to a great advantage as aggregate and insulating material in the construction industry. Early uses of perlite were related exclusively to the construction industry, which now consumes about 60% of the domestic production. The primary use of perlite now is as aggregate in insulation boards. Other uses of perlite in 1971 were as aggregate for plaster, horticultural aggregate, low-temperature insulation (cryogenics), and concrete. Because of its low thermal conductivity ("K" factor), high adsorption of sound, low bulk density, and fire resistance, perlite aggregate plasters hold many advantages over conventional plaster. Perlite aggregate plaster lends itself to machine applications, dries quickly, and has relatively high elasticity which reduces cracking after drying. These same features make perlite useful as aggregate in portland cement concrete and asphalt concrete for construction wherever weight reduction, insulation, and acoustics are of prime importance. Perlite-portland cement concrete offers up to 20 times more thermal insulation than conventional concrete, and because of this it finds wide application in roof decks and floor fill in multistory buildings, in

Jan 1, 1975

By Charles Prasky

ABOUT five years ago the Bureau of Mines began a study, at Minneapolis, of the various methods for beneficiating the low-grade manganese deposits of the Cuyuna range. Several samples of green carbonate slate from the Cuyuna range, containing about 7 pct Mn and about 28 pct Fe, were obtained for this study. The component minerals in the carbonate slate formation were so intimately associated that mineral dressing methods were not suitable for concentrating manganese to a ferrograde product. Although upgrading of manganese and iron minerals has been effected by flotation methods, it appears that manganese cannot be separated from iron except by chemical means. Because the flotation studies at Minneapolis were carried out simultaneously with the hydrometallurgical studies, only crude slate was available for process testing. An important economic consideration in selecting any one of the several chemical methods proposed for recovering ferrograde manganese is the availability of the chemical reagent. Fortunately, large tonnages of sulfur are available on the Cuyuna range in low-grade pyrite and pyrrhotite deposits that are readily concentrated by flotation to a suitable feed for a sulfide roasting furnace as indicated by a Bureau of Mines investigation in 195 0-1951.1 The roasted residue from the sulfide concentrates is a potential source of marketable iron oxide. Therefore, if these sulfide deposits were employed in recovering manganese, utilization of two heretofore unused mineral deposits would be accomplished. Laboratory investigations of several proposed leaching processes were made as a preliminary step in the investigation of hydrometallurgical methods for the treatment of Cuyuna carbonate slate using sulfur as a chemical reagent. From results obtained in the laboratory tests, these leaching processes did not appear entirely suitable for treating Cuyuna carbonate slate. The method developed at the North Central Experiment Station and selected for a more intensive pilot-plant investigation has been termed the differential high-temperature sulfatizing process. Essentially, this sulfatizing process consists of the following steps, described in the order in which the small-scale pilot-plant investigations were made. The first and perhaps most significant step in the process consists of a sulfate roast. Carbonate slate is roasted in an atmosphere of sulfur dioxide gas and air. The overall chemical reaction for converting manganese carbonate to a sulfate at a high temperature in a sulfur dioxide atmosphere follows MnCO8 + SO2 + 1/2 0, = MnSO4 + CO2 (H077°O = —64,180 cal per g mol) .' The need for concentrated sulfuric acid is avoided. Fine grinding is not essential. Removal of carbon dioxide from the slate during roasting produces a more porous structure and permits easier permeation by the sulfatizing gas mixture. The temperature limits for this conversion of manganese have been established as 600" and 850°C. Iron sulfate is unstable and is not formed at these temperatures; phosphorus is not converted to a water-soluble form; and polythionates are not formed. The second step in the process consists simply of a water leach of the sulfatized product. Manganese sulfate in the sulfatized product is dissolved in water. Iron, phosphorus, and calcium remain in the leach residue as water-insoluble products. The third and final step consists of the recovery of ferrograde manganese oxide from manganese sulfate leach solution. Water is evaporated from the leach solution, and impure monohydrate crystals of manganese sulfate are recovered. The moist crystals are formed into pellets or extrusions and thermally decomposed to produce a ferrograde manganese

Jan 1, 1958

By Gerald C. Mathis

FERGUS County, Mont., shown in Fig. 1, is known for its once famous gold mines near the old towns of Gilt Edge, Maiden, and Kendall. But at Heath, a small farming community near the foothills of the Snowy Mountains, thousands of tons of gypsum have been mined since 1916. The value of the gold taken from the mines of Fergus County runs into millions of dollars; the value of the products made from the gypsum of the Heath mine is also in the millions. The gypsum mine will continue to produce for many years, while the gold mines are closed today. The Heath gypsum mine was developed by the Northwest Gypsum Co. in 1916. The products of the small mill built by this company were plaster, agricultural gypsum, and raw gypsum for cement manufacturing. The United States Gypsum Co. prospected the adjacent property in 1916 and 1917 by means of two adits and some exploration drill holes. During World War I, the company abandoned operations at Heath, but again became active in this area in 1928 hen it purchased all the property of the Northwest Gypsum Co. A long range program of expansion was begun with the building of a block plant and the purchase of additional land and mineral rights. A modern wall board plant was built in 1936. When the old wooden mill purchased from the Northwest Gypsum Co. burned in 1937, an all-metal calcining plant located at Blue Rapids, Kansas, was dismantled, moved to Heath, and erected on the site of the mill. In August 1951 a new mine was opened 3000 ft north of the mill. Rock is conveyed from the mine to the mill by an 18-in. belt conveyor. The Heath gypsum deposit lies at the base of the Ellis formation of Jurassic Age. The Ellis at Heath lies unconformably on the black fissle shale of the Heath formation of the Big Snowy Group, which is Mississippian in age. The strike of the gypsum bed is N45°E and the dip approximately 3" NW; the regional strike and dip of the area. The gypsum lies in a series of six layers separated from each other by thin seams of shale. The lower layer is composed of' gypsum and shale intermingled and is not of commercial grade. The upper five layers are high in purity, but only the middle four layers are mined on the advance, as the top layer is left for roof support. This top layer is mined on retreating operations at the same time the pillars are robbed. Total thickness of the gypsum layers varies from 12 to 14 ft. Fig. 2 shows the average thickness and arrangement of the layers. Mining Methods The mine was originally developed by driving an adit into the gypsum horizon. The Northwest Gypsum Co. mined in the top four layers, the top layer being split, leaving about 12 in. for roof support. A modified room and pillar method was used: entries were 15 ft wide and rooms varied between 20 and 30 ft and were turned on 90" from the entries. Crosscuts between the rooms left pillars from 10 to 20 ft square. The rock was loaded by hand into 1-ton mine cars and pulled to a central gathering point by mules; from the gathering point, mules or horses were used to pull the string of cars to the mill tipple. This method was continued by the United States Gypsum Co. from 1928 to 1937.

Jan 1, 1954