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By W. L. Hill, W. H. Armiger, S. D. Gooch

The physical properties, chemical behavior under thermal treatment, and fertilizer value of fluorine-containing pseudowavellite (hydrous calcium aluminum phosphate) that occurs as phosphate clay admixed with quartz sand in an extensive deposit near Bartow, Fla., were determined by experiments in laboratory, pilot-plant, and greenhouse. When the mineral was heated at 500°C, 80 pct of the phosphorus become citrate soluble. The heated product, however, deteriorates markedly under moist conditions such as obtain in the soil. EXTENSIVE beds of a soft aluminiferous phosphate lie in the Bartow-Pembroke region of Florida. Although the extent of the deposit is unknown, it is thought that the equivalent of at least five million tons of material containing 25 pct P,Os exists on one large mine property alone, and soft phosphates similar in nature are known to occur elsewhere in the state. This aluminum phosphate, unlike fluorapatite, is rendered fairly soluble in neutral ammonium citrate solution merely by heating it at a temperature below 600 °C, a property made the basis of a process patent by the junior author.' The possibility of producing an available form of phosphorus from what has hitherto been a worthless natural phosphate prompted the Bureau of Plant Industry, Soils, and Agricultural Engineering to make a brief study of the Pembroke phos- phate during the war years with a view towards determining the optimal temperature for heat treatment and the reactions involved in the process. The results of this study supplemented by data and information furnished by the junior author are presented in this paper. Description of Natural Phosphate: The phosphate with admixed quartz sand and siliceous matter occurs as a low-grade (8 to 9 pct P2O5) clay-like material that can be beneficiated cheaply by making a water separation of the very fine material from the sand, floating off the fine material, settling the suspension to a thick slurry, and finally de-watering the slurry by vacuum filtration followed by drying. The product dried at 100 °C contains about 16 pct water and 25 pct P2O5, about 1/12 of which is citrate soluble. Partial analyses of representative samples of the crude ore and corresponding concentrate are given in table I. The concentrate is light yellow in color and even after being dried at 100°C sticks very noticeably to laboratory grinding and screening equipment. Under the microscope the ground material is predominantly light brown crystalline aggregates with index of refraction near 1.61. The principal phosphate mineral constituent was identified as pseudo-wavellite with admixed phosphosiderite.2 Pseudo-

Jan 1, 1951

By R. K. Waring, E. C. Truesdale

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By E. C. Truesdale, R. K. Waring

The Research Division of The New Jersey Zinc Company (of Pa.) has conducted, over a period of years, numerous tests of the reducibility of various zinc ores and the reactivity of various kinds of coal, using a number of different experimental methods. Most of these tests have involved the reduction of mixtures of ore and coal. In such cases the following simultaneous reactions are believed to be mainly responsible for the production of zinc, as was shown by Bodenstein1 some years ago: ZnO+ CO = Zn + CO2 [1] C + CO2 = 2 CO [2] Each of these reactions is dependent upon the other for the supply of CO and CO2 , respectively, and the over-all rate of formation of zinc vapor will be determined by the slower of these two reactions. An analogous pair of reactions sometimes of importance is: ZnO + H2 = Zn + H2 O [31 C + H2O = CO + Ha [4] While it is possible to obtain an indication of the relative reducibility of various ores, or of a fine versus a coarse ore, by testing them with a given coal, and while coal reactivities may be measured in a corresponding manner, a more direct determination of relative reaction rates is possible by carrying out the desired reactions, such as I and 2, separately and under reproducible conditions. It is one purpose of this paper to present some of the results that have been obtained by the latter method. C. G. Maier2 discusses the relative rates of reactions I and 2 and concludes that while at relatively low temperatures reaction I is faster than reaction 2, this difference becomes less with increasing temperatures, although at smelting temperatures reaction I is still the faster. He also says (p. 48), "At temperatures . . . between IIOO° and I3oo°C., . . . the zinc oxide reduction reaction is intrinsically more rapid than its physical limitations; that is, it is limited by gas diffusion rates." In the course of numerous reactivity tests involving the separate use of reactions and I and 2, we have obtained data that show by direct experiment, we believe for the first time, the correctness of Maier's statements concerning these reactions. We also include data on the relative rate of reaction 3, involving reduction by hydrogen. Finally, some interesting results obtained by carrying out the reduction of a zinc ore-coal briquet in streaming atmospheres of nitrogen, carbon monoxide and hydrogen, respectively, are presented. *

Jan 1, 1943

By Howard I. Smith

THE mineral trona was discovered on Government land in 1938, about 18 miles west of the town of Green River, Wyo., in the core of the John Hay, Jr., well, a test well drilled for oil by the Mountain Fuel Supply Co. in sec. 2, T. 18 N., R. 110 W., sixth principal meridian. Although no oil or gas was reported, the drilling led to a discovery of great potential economic importance and exceptional scientific interest. Trona is a relatively rare mineral found at various places in playa deposits but not previously found at any great depth. It is composed of hydrous sodium carbonate and sodium bicarbonate (Na2CO3.NaHCO3.2H20). Pure trona contains the equivalent of 70.35 per cent of sodium carbonate. Total sodium computed to carbonate times 1.42 equals the percentage of trona in the absence of other sodium carbonate minerals in the sample. ANALYSES Two short pieces of core sent to the author a few days after the completion of the Hay well were analyzed by R. C. Wells[t] and found to be exceptionally pure trona. A brief article on this discovery has already been published.1 Arrangements were then made through W. T. Nightengale[$] for the author to inspect and sample the core. The company log of the well included notations of sodium salt crystals from a depth of 1190 to 1820 ft. Not being able to identify all the minerals present, the author selected several specimens of the core for petrographic examinations and sampled the sections of trona for analysis. J. J. Fahey, of the Geological Survey, examined the specimens and reported most of the crystals to be a new anhydrous sodium carbonate and calcium carbonate mineral (Na2CO3.2CaCO3), which he named shortite,2 after Maxwell N. Short.* He analyzed the samples of trona, with the results shown in Table I. [ ] In addition to the 10 ft. I in. of trona in the first section, it is reasonable to assume that the 9 ft. 8 in. for which no core was available for sampling is either mostly trona or some other soluble salt, but it should not be included in calculating reserves. In the part of the core between 1590 ft. 3 in. and I600 ft. 4 in. the material insoluble in cold water, amounting to about 5 per cent, was estimated petrographically to contain 70 per cent clay, 25 per cent shortite, and 5 per cent pyrite. ACCOMPANYING MINERALS Fahey later secured about 600 ft. of the core for a detailed examination and study

Jan 1, 1942

By Thomas F. Bates

ANALYSIS of the chemical and structural differences in minerals often results in a better understanding of the differences in the geological conditions under which they were formed. The minerals in the kaolinite group differ in the amount of interlayer water and in the nature and amount of ordered and/or random shifting of each 1:1 layer with respect to those above and below it. This paper is a progress report resulting from research on the morphology, structure, and origin of fine-grained minerals, supported by Contract N6onr26914 with the Geophysics Branch of the Office of Naval Research. The purpose of the paper is to present data obtained in the laboratories at The Pennsylvania State College and elsewhere, which reveal some of the details of structure of the minerals in the kaolinite group, and to suggest a number of interpretations that bear upon the conditions of origin of these minerals. Be¬cause most of the work in this investigation thus far has been concerned with the relationships of kaolinite, halloysite (4H2O; endellite), and halloysite (2H2O), must of the discussion deals with these members of the group. The first step in the analysis of the differences in two sets of geological conditions is an evaluation of the differences in the minerals that result. Thus the chemical differences between the montmorillonite and the kaolinite clays corroborate other evidence in support of the view that the montmorillonites are commonly formed when solutions are alkaline and leaching poor, while kaolinite usually is associated with acid solutions and good drainage condi¬tions. It is obvious that the greater the differences in the minerals, the more divergent may be the conditions that give rise to them and the more readily one condition can be distinguished from the other. In the kaolinite group, differences between individual members are small, therefore the differences in condition of origin are presumably subtle and difficult to define. At the same time, the very fact that the minerals differ only slightly makes them more sensitive indicators of the exact conditions under which they and the minerals associated with them were formed. Since clay minerals are being used more and more to evaluate the nature, value, and mode of formation of economic mineral deposits, an attempt to define these subtle differences would appear worth while. For purposes of the present discussion, the minerals nacrite, dickite, kaolinite, the so-called "fireclay mineral," halloysite (4H2O), halloysite

Jan 1, 1952

By E. S. Wheeler

The conversion plant of the Clirnax Molybdenum Co. is at Langeloth, Washington . County, Pennsylvania, approximately 30 miles west of Pittsburgh. The molybdenite concentrates converted originate in the company's mine and mill at Climax, Co1orado.l They are delivered to the Langeloth plant by rail packed in 175-lb. bags. War production of concentrates at the mill started in 1918 but it was not until about 1920 that any peacetime uses of the metal began to develop. Early conversion of Climax concentrates was mainly into ferromolybden um, produced for the company by a custom smelter. Chronology of Plant Development In 1924 a small hand-rabbled roaster was built at Langeloth, the roasted concentrates being used principally in the production of calcium molybdate by a conventional wet method. The size of the original plant is indicated by the fact that during 1925 about 400,000 lb. of molybdenum was converted. In 1925-1926, a multiple-hearth roaster was erected (12-ft. 0.d. 8-hearth Nichols-Herreshoff); also the first experimental ferromolybdenum was produced at Langeloth. At this time sa.1cium molybdate was produced in the furnace by a process to be described. With continued interest in and increased use of molybdenum, it was necessary to arrange for enlargement of plant facilities. Although only one 12-hearth 16-ft. 0.d. roaster was erected at this time (1929), plans were prepared for a duplicate unit, which was completed in 193 5, giving a potential roasting capacity of some 16,000 lb. Mo per day under the then prevailing roasting practice. Shortly after this second unit had gone into production, increased demand overtaxed the plant, and as a result two 12-hearth 18-ft. 0.d. roasters were placed in operation in 1936 and 1937. This gave the plant a potential roasting capacity of 40,000 to 50,000 lb. Mo per day, and necessitated major changes in auxiliary handling equipment as well as improved facilities for producing ferromolybdenum. Following the introduction (1938) of a new product—molybdic oxide briquets— and because of the constantly growing demand for molybdenum, plant facilities were again enlarged in 1940 and 1941 by the erection of two 16-hearth 18-ft. 0.d. roasters. These two new units, along with a change in roasting practice, brought the potential roasting capacity to 150,ooo to 190,000 Ib. Mo per day, based on about 15 lb. per sq. ft. of hearth area. Other departments of the plant have necessarily grown, until today the plant is modern throughout and completely mechanized, with equipment geared to produce marketable products as follows:

Jan 1, 1944

By C. W. Hamilton

In the production of crude petroleum for the year 1930 Venezuela again maintained its world rank of second only to the United States. During the latter months of the year Russia forged ahead of Venezuela in daily rate of production, and from the present outlook will probably rank second among the oil-producing countries of the world in 1931. It is now believed Venezuelan production has passed its peak. The producing fields of the Bolivar coastal district, along the east side of Lake Maracaibo, continue to be the principal source of supply. Such fields as Lagunillas, Mene Grande and La Pas were not produced to capacity throughout 1930. During the year, three new fields entered into commercial development: The Rio Tarra field in the District of Colon, State of Zulia; the El Mene de Salto field in the District of Acosta, State of Falcon and the Quiriquire field, District of Piar, State of Monagas. For 1930 the total crude production of Venezuela was approximately 137,424,000 bbl. as compared to 137,739,000 bbl. during 1929, or a decrease of 315,000 bbl. During the past year exports of crude from Venezuela amounted to 137,8.50,000 bbl. as against 130,044,000 bbl. exported during 1929. Crude oil in field storage decreased from 14,138,-000 bbl. at the beginning of 1930 to 9,600,000 bbl. as of Jan. 1, 1931— present crude stocks fill about one half the field tankage available. Drilling operations in the producing fields declined sharply but throughout the year there was maintained a satisfactory potential reserve in the shape of proven territory and closed-in producers. Of the 2555 wells which have been completed in Venezuela, 1571 wells were in production on Jan. 1, 1931. The status of these present producing wells may be classified as follows: flowing 652, pumping 170, gas-air lift 193 and closed-in 556. The ratio of closed-in wells to producing wells declined in 1930, while the number of wells produced by artificial means increased materially. In the Bolivar coastal fields there is now observed a marked decline in gas volume and well-head pressure. Lago Petroleum Corpn. and Venezuela Gulf Oil Co. each have under construction electric plants designed to generate power for pumping wells by electricity. The first units of these plants will be placed in conlmission in the early spring of 1931. Venezuela Oil Concessions, Ltd. has installed a number of stenrn-

Jan 1, 1931

By Ernest G. Enck

"The Rockets' Red Glare" of the Fourth of July is produced by strontium compounds. However, strontium has a number of less spectacular uses; i.e. in, or in connection with, the manufacture of ceramics, caustic soda, glass, railway and truck signal flares, beet sugar and steel. The principal ore of strontium for use both as the mineral and for production of compounds is celestite (SrSO4). This mineral varies in color from white to pink or blue depending on presence of impurities. It has a hardness of about 3.5 and specific gravity of 3.9. It is brittle and has perfect basal and prismatic cleavages. The high grade ore is obtained from England, hence it has become the standard for all other producing areas. (See analyses, Table 1.) The most objectionable impurity in English celestite is iron, coming mostly from adhering clay. On the other hand, Mexican celestite, while no higher in strontium sulfate content, is extremely low in iron (less than 0.2 pct), hence it is more desirable for certain uses. Most of the celestite in Spain and in the United States is high in calcium and barium, and commonly high in iron, and requires some form of beneficiation in order to be equal to English ore. The natural carbonate (SrCO3), or strontianite, is less important than celestite as a source of strontium, because it is less abundant and is not so widespread in its occurrence. Furthermore, it generally occurs with calcite (CaCO3) and lead sulfide (PbS), and for most uses these impurities are detrimental. This mineral is generally white or yellowish, forming needle-like crystals. It has a hardness of about 3.7 and a specific gravity of 3.68-3.8. The mineral is brittle and has an imperfect cleavage. A typical analysis of German strontianite is shown in Table 1. [ ] Distribution of Deposits UNITED STATES Occurrences of strontium minerals are known in Arkansas, Arizona, California, Illinois, Ohio, Pennsylvania, Tennessee, Texas, and Washington. Celestite occurs in the Vulture Mountains, Maricopa County, Arizona in beds three to ten feet thick associated with sandstone, gypsum, and barite. Because of the low strontium content, approximately 86 pct SrSO4, it has no commercial value. A large deposit of celestite occurs in San Bernardino County, California, in the Cady Mountains near Argus Station, about eight miles west of Ludlow. The celestite here is interbedded with shaly and clayey tuff in a zone about 300 ft thick. Massive, finely crystalline ore has been recovered with an analysis

Jan 1, 1960

By Pol Duwez, Paul Pietrokowsky

The crystal structure of the compound TisGeS has been determined from X-ray powder diffraction data. Related silicon and tin compounds have been found to be isomorphous. Unit cell dimensions, axial ratios, and parameters for equivalent atomic positions are given. THERE is, at present, only meager information pertaining to the solid state reactions of titanium with the elements in group 4B of the periodic table (silicon, germanium, tin, and lead). The only two compounds whose crystal structure has been established are TiSi² and TiGe² (references 1 and 2 respectively). These two compounds are isomor-phous and have an orthorhombic symmetry D242h— Fddd. The titanium-rich regions of the constitution diagrams of titanium-silicon, titanium-tin, and titanium-lead have been investigated by Craighead et al.³ While valuable information concerning the alpha solid solubility of these three elements in titanium was obtained, no light was shed on the existence or nature of the titanium-rich compound in these systems. The present study is concerned with the crystal structure of the intermediate phases Ti5Si ?, Ti³Ge³, and Ti5Sn³, which were found to be isostructural. The alloys were prepared by mixing the pure metal powders in the desired proportions, pressing the mixture into pellets, and melting them in an electric arc furnace in the presence of a helium atmosphere.& After melting, the specimens, weighing approximately 5 g, were sealed in evacuated quartz vials, homogenized at 1038°C for three days, and quenched from that temperature. Powder diffraction patterns were made with a 143.2 mm diam Debye-Scherrer X-ray camera in which the Ievins and Straumanis film arrangement was utilized. Filtered copper radiation was used throughout the entire investigation. A study of the powder patterns of a series of alloys of various compositions indicated the presence of a compound around a composition corresponding approximately to a ratio of 3 titanium to 2 silicon, germanium, or tin. From a visual examination of the diffraction patterns, it was evident that the silicon and germanium alloys were iso- morphous. For small angle reflections, the powder pattern of the tin compound was analogous to that of the silicon and germanium compounds, but after the first ten reflections, the similarity was no longer clear. The powder pattern of the germanium compound was selected for indexing, since it exhibited a weak small angle reflection and clearly resolved doublets in the back-reflection range. Good agreement between observed and calculated values of (1/d)² was found by indexing the pattern on the basis of hexagonal symmetry. For the hexagonal system:

Jan 1, 1952

By D. L. Murphy

As the world's demand for iron ore increases and available sources are depleted, increasing attention will be centered on deposits in the Quebec and Labrador portions of the Labrador Trough. Improvements in the beneficiation of low grade iron ore stimulate exploration for deposits amenable to concentration. This study is centered on the Mt. Wright-Lake Carheil area, lying between Wabush Lake and Mt. Reed in Quebec. Described in detail are the general lithology, structural and economic geology, and mineralogy of the iron-formation. The iron ore province of Quebec and Baffin Island extends from the southern shore of Baffin Island southeasterly through the Labrador Trough to Matonipi Lake, approximately 185 miles northwest of Seven Islands. (See Fig. 1.) Future geologic field studies will very likely extend the limits of the province to include the ferruginous and associated rocks of the Lake Mistassini area. At present, only the deposits near Knob Lake and Lake Jeannine (Mt. Reed) have been brought into production although in the near future several other properties including those at Wabush Lake will commence operations. Within the next decade or so, as the world's demand for iron ore increases and available sources are depleted, this region will undoubtedly become a major mining district. Initial reports of iron-rich rocks in Labrador date back to the investigations undertaken by A. P. Low near the turn of the century. During the ensuing years the country was prospected chiefly for precious and nonferrous base metals because of its inaccessibility and the low tenor of the iron ore. In 1945 an evaluation of the direct shipping ores near Knob Lake indicated that sufficient reserves were present to justify the enormous capital expenditure required to bring the deposits into production. Initial open-pit mining began in 1954 following the construction of a townsite, a 360-mile long railway to Seven Islands, and an elaborate loading dock. Recent improvements in the beneficiation of low-grade iron ore have stimulated widespread exploration for deposits amenable to concentration, particularly along the southwest extension of the Trough. The Mt. Wright-Lake Carheil area, bounded by longitudes 66O45' and 67 30' west and latitudes 52 30' and 52 45' north, is a nearly rectangular tract of slightly less than 500 sq miles. It is in Saguenay County, 174 miles north-northwest of Seven Islands (see Fig. 1). Except for the periods of the spring breakup and the fall freeze up, the area is readily accessible by air.

Jan 1, 1962

By T. D. Guldem, J. L. Kaae

ALLOYS with nominal composition of 45-Fe 35-Ni 20-Cr, ASTM-B-163, known under the commercial names of Incoloy 800 and Sanicro 31 (Alloy 800), are often employed at elevated temperatures for extended periods. Therefore, knowledge of the aging behavior of these alloys is of considerable importance. Significant decreases in ductility and increases in yield strength have been observed in the 45-Fe 35-Ni 20-Cr alloys containing about 0.4 pct Ti and 0.4 pct A1 after long-term aging at 540" to 700"~."~ However, no direct evidence has been presented for precipitation phenomena that might result in such changes. Strengthening effects have been attributed to the effects of local or-dering.3 Since y' precipitation (Ni3A1, Ti) is known to occur in similar alloys which contain more titanium and aluminum,4-7 it was decided to explore the possibility that y' might precipitate in these alloys and might be responsible for the changes in mechanical properties on aging. This note reports some observations of two distict types of matrix precipitates made by means of transmission electron microscopy, in a 45-Fe 35-Ni 20-Cr alloy containing 0.31 pct Ti and 0.4 pct Al. The steel used in this investigation was obtained from the Sand-vik Steel Works; it is designated Sanicro-31 (Alloy 800). The chemical composition of the alloy is given in Table I. Aging of solution-treated material at 700" and 800°C for 130 and 100 hr, respectively, produced the matrix precipitates shown in Figs. l(a) and l(b). It is apparent from these micrographs that the precipitate particles occurred in the form of thin square plates parallel to the matrix cube planes. Extraction replication and selected-area electron diffraction showed that the precipitates were M23C6. Coherency strains, consistent with the semicoherent nature of small M23C6 precipitates,' were evident for certain imaging conditions. In addition to matrix precipitation, preferential precipitation of M23C6 on dislocations was common, as has been reported previously for austenitic stainless steels.'" Specimens aged for longer times (-300 hr) at 700°C exhibited a different type of coherent matrix precipitate in addition to the M23C6. An example is shown in Figs. 2(a) and 2(b). In addition to the few large M23C6 precipitates, small precipitates exhibiting strain contrastl0,ll are present. The "line of no contrast" of the strain field of a given precipitate lies along differ-

Jan 1, 1970

By Howard I. Smith

THE mineral trona was discovered on Government land in 1938, about 18 miles west of the town of Green River, Wyo., in the core of the John Hay, Jr., well, a test well drilled for oil by the Mountain Fuel Supply Co. in sec. 2, T. 18 N., R. 11o W., sixth principal meridian. Although no oil or gas was reported, the drilling led to a discovery of great potential economic importance and exceptional scientific interest. Trona is a relatively rare mineral found at various places in playa deposits but not previously found at any great depth. It is composed of hydrous sodium carbonate and sodium bicarbonate (Na2CO3.NaHCO3.2H2O). Pure trona contains the equivalent of 70.35 per cent of sodium carbonate. Total sodium computed to carbonate times 1.42 equals the percentage of trona in the absence of other sodium carbonate minerals in the sample. ANALYSES Two short pieces of core sent to the author a few days after the completion of the Hay well were analyzed by R. C. Wells† and found to be exceptionally pure trona. A brief article on this discovery has already been published.1 Arrangements were then made through W. T. Nightengale‡ for the author to inspect and sample the core. The company log of the well included notations of sodium salt crystals from a depth of 1190 to 1820 ft. Not being able to identify all the minerals present, the author selected several specimens of the core for petrographic examinations and sampled the sections of trona for analysis. J. J. Fahey, of the Geological Survey, examined the specimens and reported most of the crystals to be a new anhydrous sodium carbonate and calcium carbonate mineral (Na2CO3.2CaCO3), which he named shortite,2 after Maxwell N. Short.* He analyzed the samples of trona, with the results shown in Table i. [ ] In addition to the 10 ft. I in. of trona in the first section, it is reasonable to assume that the 9 ft. 8 in. for which no core was available for sampling is either mostly trona or some other soluble salt, but it should not be included in calculating reserves. In the part of the core between 1590 ft. 3 in. and 1600 ft. 4 in. the material insoluble in cold water, amounting to about 5 per cent, was estimated petrographically to contain 70 per cent clay, 25 per cent shortite, and 5 per cent pyrite. ACCOMPANYING MINERALS Fahey later secured about 600 ft. of the core for a detailed examination and study

Jan 1, 1942

W. D. BRENNAN,* Cheyenne, Wyo. (written discussion?).-My experience has been that, where possible, it is preferable for each foreman to employ his own men, rather than to have them handled through an employment bureau. The fact that each foreman comes into direct contact with the man before he is put to work gives him an opportunity to choose, at certain times, the kind and class of men that he wishes. Where possible, after a man is employed he is sent to a central office where a complete history of each individual is kept on a card. If a man has previously been in the employ of the Company, his history can be obtained from this card, and if for any reason he is not wanted he can be refused work at the time he reports to, the central office. In connection with Workman's Compensation costs, we in Wyoming feel that although the rates of compensation paid may in some cases be rather low our law works satisfactorily. As the State and the number of employees are small, compensation cases are handled through Judges of the various District Courts. In the State Treasurer's Department, a few clerks were added to look after the handling and issuing of warrants and compiling of statistics. Most of the large employers have an arrangement by which a joint claim and assent, specifying the amount of compensation due, is made tip by the employer and signed by the workman. This is forwarded, to the Judges so that personal investigation of individual cases is not necessary. In this manner, compensation is promptly received and' overhead expenses of operation of the law is kept at the minimum. The law requires each employer to pay into the State Treasury, for the benefit of the industrial fund, a sum equal to 1.5 per cent. of the money earned by each employee, engaged during each calendar month of such employment. Each employer contributes monthly, unless the sum heretofore contributed, after deducting all payments made on account of injuries to his employees, shall equal a full 1.5 per cent. of his annual pay roll, computed by multiplying his current monthly pay roll by twelve, and shall likewise be not less than ($5000). It has been found during the years that this law has been in effect, that a number of the larger employers have been exempt from payment for from five to eight months per year, so that in some cases, even in coal nines, industrial insurance has cost less than 0.75 per cent.

Jan 3, 1919

By R. E. Somers

1. INTRODUCTION 1. Location, Topography, and Climate The Burro Mountains are located in the southwestern part of New Mexico, in Grant County. The group is made up of two distinct moun-tain masses, known as the Little Burros and the Big Burros, the former lying about 6 miles southwest of Silver City-, and the latter about 9 miles farther in the same direction. They are separated by the valley of the Mangas River, a tributary of the Gila, and a stream only in name, except after a heavy down-pour of rain. . The Little Burros attain an elevation of 6,625 ft. above sea level, and the Big Burros 8,054 ft., with the surrounding country averaging about 6,000 ft. To the south of these mountains stretches the desert plain, while to the north are the more frequent elevations of the mountainous country.

Jan 5, 1915

By C. A. Stickels, C. M. Yen

Secondary recrystallization was investigated in vacuum-melted electrolytic iron to which 70 pm N was vacuum-meltedadded. The secondary texture is "near {554}<225>" for material cold-rolled 75 to 90 pct, the sharpness of the texture increasing with increased rolling reduction and with decreased annealing temperature. At reductions of 95 and 97.5 pct the secondary texture is &apos;"near {322)(296)". Both secondary orientations also exist as major components of the primary re-crystallization texture. Development of a strong "near {554) (225)" secondary texture appears to depend on the evolution of the Primary texture to a transition texture depleted in orientations near the secondary orientation before the onset of secondary growth. A variety of qualitative experinzents have been used to show that nitrogen is important in limiling primary grain growth. The presence of nitrogen does not seem essential for the establishment of a transition texture, but a loss of nitrogen during annealing may facilitate growth of grains in the secondary orientation. Secondary grains we shown to form initially at the specimen surface. This is not thought to indicate that surface energies are important in the growth process. It is proposed that the quasi-two-dimensional character of surface grains permits discontinuous growth parallel to the surface before secondary growth of interior grains is possible. An earlier study of recrystallization textures in 90 pct cold-rolled electrolytic iron showed that secondary recrystallization occurred after annealing for several days at 700C1 This type of secondary recrystallization, which had not been reported previously, results in the formation of a strong texture, best described by the indices "near {554}(225)". The purpose of the present work was to investigate the effect of various processing variables on secondary recrystallization in this material and determine the mechanism of secondary grain growth. LITERATURE REVIEW An understanding of the mechanism of a secondary recrystallization process depends on knowing: 1) how grains in the secondary orientation come to be in the primary recrystallization texture; 2) why normal grain growth does not occur; and 3) what factors determine the strength of the secondary texture. For secondary growth of grains of a particular orientation, a certain minimum fraction of the grains must be in that orientation after primary recrystallization. This requirement is apparently satisfied "naturally" in certain systems, i.e., when the primary texture obtained by rolling and recrystallizing material initially randomly oriented contains a sufficient fraction of primaries in the secondary orientation. However, in other cases, e.g., {110}<001> and {100}<001> secondary growth in silicon iron,2 it is necessary to enhance the fraction of primary grains in the secondary orientation by rolling and recrystallizing textured material. In the present case, the "near {554}<225>" orientation is contained within the spread of orientations found in the primary recrystallization texture of iron or bbc iron-base alloys. In systems where the main driving force for secondary growth is the reduction in total grain boundary energy, secondary growth is observed only when normal grain growth is minimized. Four ways in which normal grain growth can be limited are: 1) Limitation by a strong primary texture. When a very strong primary texture consisting of a single component or twin-related components develop, most primary grains are separated from one another by relatively immobile small-angle grain boundaries. The classic instance of this is secondary growth into the primary cube texture in some fcc metals. 2) Limitation by precipitates. Precipitates present in the proper volume fraction with a suitable dispersion will limit primary grain growth. The role of MnS inclusions in impeding normal grain growth in Si-Fe is well-documented.5 3) Limitation by sheet thickness. Normal grain growth slows drastically when the mean grain diameter is of the same order as the sheet thickness. This effect has been used to obtain secondary recrystallization in thin sheets of high-purity silicon iron.&apos; 4) Limitation by solute impurities. It is well-established that certain impurity elements in solution can have a large effect on grain boundary mobility.&apos; However, there does not seem to be any secondary recrystallization process in which primary grain size stabilization has been shown to be due to the drag exerted on grain boundaries by dissolved impurities. In certain systems, e.g., secondary recrystallization in silver,&apos; the means by which normal grain growth is limited has not been identified, and solute-impurity limitation might be suspected. In order to understand the factors which determine secondary texture strength in three-dimensional growth, it is necessary to examine in more detail the current picture of general secondary recrystallization processes. Following Cahn,9 it is assumed that the primary grains have a range of sizes and that secondary growth of one of the large grains in this distribution is possible when it exceeds a critical size with respect to its neighboring grains. The critical size depends on the ratio ?S/?p, where ?s is some sort of average grain boundary energy between the potential secondary and the primary grains and ?p is some sort of average grain boundary energy between primary grains. For a constant primary grain size, the critical size for secondary growth increases as ?$/?p increases. May and Turnbull5 have incorporated the

Jan 1, 1969

By D. T. Peters

To better understand the Co-Mo interaction in maraging steels, the precipitate reversion behavior of two alloys closely related to the 18 Ni-250 grade has been studied. The reversion experiment is carried out by aging at a low temperature, T1 (preaging temperature), for some period of time and then aging at a higher temperature, T2, called the reversion tetnperature. Aging and reversion tmzperatures used were in the range 679 to 1050°F. Reversion is marked by an increase in resistivity and a decrease in hardness. It teas found that some reversion took place at all cornbinations of T1 and T2 but that pronounced rei3ersion resulfed for an Fe-18 pct Ni-5 pct Mo-8 pcl Co alloy exposed to preagz&apos;ng&apos; temperatures at or below 850°F. A similar alloy not containing cobalt exhibited no such discontinuity in reversion behazior with TI. The results are interpreted in terms of two types of molybdenum-rich precipitates, one nucleated at dislocations and the other in the matrix. The increased supersaturation resulting from the presence oj- cobalt evidently provides sufficient energy to nucleate the matrix phase. Anotnalies in the temperature dependence of the resistivity decrease and peak hurdness in the Fe-18 pct Ni-5 pct Mo-8 pct Co alloy as a junction of aging temperature noted in an earlier study are explained on this basis. SEVERAL investigatorsl-9 have studied the details of the precipitation-hardening reaction of the maraging steels. The great majority of conclusions have been drawn from transmission electron microscopy. Although much has been learned by this method, alternate techniques which will give information earlier in the aging process are needed for a more complete understanding of the series of precipitation steps probably involved in the aging reaction. Peters and cupp&apos;&apos; have recently shown, by measurements of the kinetics of precipitation, that an 18 pct Ni-Co-Mo maraging steel shows a distinct change in precipitation behavior at aging temperatures below 850°F. The results were interpreted in terms of the existence of two types of precipitates at low aging temperatures. Only one precipitate type is present at higher aging temperatures. The low-temperature precipitate was found to be a particularly effective strengthener. No evidence for the additional low-temperature precipitate was found in the 18 pct Ni-5 pct Mo ternary alloy. The object of this investigation was to study further the characteristics of the two types of precipitates and the interaction between cobalt and molybdenum characterizing this system. Some preliminary experiments indicated a difference in reversion behavior in specimens aged above and below 850°F. This suggested that knowledge of the reversion behavior might shed some light on these two questions. Hardy and Heal11 have defined reversion as the loss of hardness, electrical conductivity, or other properties caused by heating for a very short time at temperatures above the aging temperature. The precipitate reversion referred to in this paper is entirely distinct from "austenite reversion" often referred to in maraging steel literature. This latter phenomenon could more accurately be called the diffusion-controlled formation of austenite. Much has been written about reversion in several of the aluminum-base binary and ternary alloys.&apos;2-16 Two explanations for reversion have been advanced. Based on the classical nucleation theory of Volmer-Weber-Becker-Doring,17 Konobeevski18 suggested that reversion was due to the size of the precipitate particles

Jan 1, 1968

By Fritz Wald, Martin Weinstein, Herbert E. Bates

ONE of the methods for preparing a fiber-reinforced composite is that of directional solidification of a eutectic melt. Its major drawback lies in the fact that the matrix in this case is a pure constituent (or a terminal solid solution of fixed concentration) and the ratio of fiber to matrix volume is fixed. Only very few, if any, pure metal matrices possess technically useful properties, and the necessity for alloying is the inevitable consequence of this fact. Nevertheless, structures similar to binary eutectic ones can be obtained in higher-order systems by pseudoeutectic reactions of a type where crystallites and a solid-solution matrix are simultaneously precipitated from a liquid.1"3 Trials to solidify such alloys directionally—the matrix consisting of a solid solution of chromium, nickel, and silicon and the reinforcing phase being Cr3C2— will be reported elsewhere.4 This note describes constitutional studies carried out primarily to determine -the position of the pseudoeutectic and further to insure that no undesirable reactions between the reinforcing phase and components of the matrix occur in the solid state at elevated temperatures. In the investigation it was specifically desired to reinforce a matrix which is as close as possible to the 80/20 Nichrome composition with Cr3C2 to insure good oxidation resistance and improve the strength at high temperatures. No konstitutional information on the quaternary C-Cr-Ni-Si svstem in the range of interest was found in the literature. Nevertheless, the two most important ternaries c-cr-Ni5 and have been completely investigated. On C-Cr-Si some investigations have been conducted,7"9 and C-Ni-Si was studied with a few alloys in the course of the present investination 9 Eight alloys were prepared to investigate the changes in the constitution of the ternary C-Cr3Ce-yNi eutectic5 with silicon contents up to 10 wt pct. Five alloys were made with varying chromium and carbon contents around compositions containing -60 to 70 wt pct Ni and 5 to 6 wt pct Si. The latter alloys were designed to locate the y(Ni-Cr-Si-C)-Cr3C2 pseudoeutectic reaction and to determine the maximum chromium content in solid solution compatible with a two-phase equilibrium between y and Cr3C2 only. The alloys were prepared from electrolyte nickel, semiconductor-grade silicon, high-purity chromium (99.999 pct pellets), and semiconductor-grade graphite. They were melted inductively in high-purity alumina crucibles under flowing argon. Twenty-gram charges were prepared and investigated by optical microscopy (including hot-stage investigations), X-ray powder methods, and electronmicroprobe analysis. The alloys were studied in the as-cast condition and also after a homogenization annealing treatment of 48 days at 900°C in evacuated quartz ampoules. The structures of all alloys based on the ternary eutectic plus silicon in the as-cast state consisted generally of an inhomogeneous solid solution and at least two other phases. Annealing of the alloys showed that the solid solution was homogenized but that an incomplete solid-state reaction had taken place in all alloys with silicon contents over 5 wt pct. This reaction is clearly visible in Fig. 1 around the large Cr3C2 crystals (gray areas). Below this concentration, the alloys consisted of a homogeneous matrix and precipitates of Cr3C2 plus graphite, Fig. 2. The Cr3C2 was entirely unreacted here. From these observations and subsequent X-ray and microprobe investigations, it was deduced that the

Jan 1, 1969

By B. D. Smith, K. H. Coats

Experiments in which calcium chloride displaced sodium chloride from four cores showed the extent of asymmetry in the resulting effluent concentration profiles. These results provided a check on how validly the mixing process is modeled by a differential (i.e., not finite-stage) capacitance mathematical model. The effluent concentration profile from two consolidated cores exhibited considerable asymmetry, while two unconsolidated cores yielded nearly symmetrical profiles. All runs resulted in breakthrough of the 50 per cent concentration significantly before one pore volume was injected. In addition, velocity appreciably affected the effluent concentration profile from a Torpedo sandstone core. The differential capacitance model matched the data significantly better than a simple diffusion model. The capacitance model allows determination of the amount of dead-end pore space in a porous matrix and the effect of velocity on the rate of diffusion into this space. An experimental program yielding insight into the physical validity of the capacitance effect is described. INTRODUCTION Axial dispersion — the mixing accompanying the flow of miscible fluids through porous media — has been the subject of many relativeiy recent studiesl-13 and a comprehensive review of the topic has been given by Perkins and Johnston.14 This dispersion is of practical interest in studies of the miscible displacement process, fixed-bed chemical reactors, and the adsorption of solutes from a flowing stream onto the surface of a porous medium. In the latter case, the effect of dispersion must be considered when adsorption parameters are determined from the nature of concentration profiles. In general, early studies of dispersion assumed applicability of a simple diffusion equation and were concerned with correlation of the experimentallv determined "effective" diffusion coefficient with system properties over a large range of the latter. Recent have been concerned with the deviations between the asymmetrical effluent concentration profiles observed and the symmetrical ones predicted by the diffusion model. In the present study, effluent concentration profiles were obtained from consolidated and unconsolidated cores. These profiles were compared with those predicted by a differential (i.e., not finite-stage) capacitance model. Solutions to the simple diffusion model, for three sets of boundary conditions, were compared with one another and with the experimental profiles. SUMMARY OF PREVIOUS WORK The reader is referred to Perkins and johnston14 for an extensive review of studies of dispersion in porous media. Many investigators have employed the simple diffusion model characterized by Eq. 1 below: The dispersion coefficient D for unconsolidated systems is correlated by u is interstitial velocity and dp is particle diameter. Since heterogeneity of the sand pack affects the mixing, this equation is also expressed as where a is proportional to the degree of heterogeneity and is about 3.5 for random packs of unconsolidated sand.l4 Eq. 3 holds for 2 For a Do homogeneous (regular) type of packing, should be 1 or less.6 Aris and Amundson6 and Carberry and Bretton consider o to be the number of particle lengths per mixing cell in the finite-stage model. Data from consolidated cores indicate dp to be about 0.36 cm for outcrop rocks, Torpedo sandstone having a reported value of 0.17 cm.15 For v /Do less than about 2, the effect of molecular diffusion must be considered and the total dispersion coeffi-

Jan 1, 1965

By Robert E. Ogilvie, Zvonimir Ban

Oxidation experiments were conducted above 600°C to investigate the oxidation products formed on the surface of MoSi2. Results are presented which indicate that minor iron impurities play a key role in the oxidation behavior of MoSi2 above 600 °C. Based on considerations of the crystal chemistry of the oxidation products, MoSi2 with rhenium and iron additions was found to be resistant to oxidation in the pesting temperature range. AS early as 1914, Honigschmidtl observed that some silicides of molybdenum exhibited high resistance to oxidation at elevated temperatures. This fact did not arouse much interest until 1950, when Kieffer and cerwenka2 examined this property in more detail. They found that Mo-Si alloys with approximately 70 pct Mo (by weight) could be heated to 1600°C in an oxidizing atmosphere without any significant damage. The surface was found to be protected by the formation of an extremely thin silica glass layer which had no tendency to spa11 during subsequent thermal cycling. In 1955, Fitzer3 discovered that even solid bodies made of MoSi2 completely oxidized within a relatively short time when exposed to the air in the temperature range from 300° to 600°C. To describe this phenomenon he proposed the name "molybdenum disilicide &apos;pest&apos; ", clearly analogous to the previously observed "tin plague" ("tin pest") which, however, arises as the result of a phase transformation. Studies performed by Fitzer and, in particular, one published recently by Berkowitz, Blackburn, and Fel-ten,&apos; comprise the most extensive research to date on the pest phenomenon in MoSi2, as far as the fundamen- tal mechanism of the process is concerned. The first of these studies revealed the existence of a crystalline phase which appeared at the surface at 750°C and dissolved in the glassy silica layer at 1150°C. The logical assumption was that this phase was some reaction product of MOO3 and SiO2. The formation of a reaction product of this type seemed probable since it had been mentioned by Glemser and Lutz6 in a paper describing their studies of molybdenum oxides; however, this assumption was later disproved.8 It is our belief that information concerning the exact nature of this crystalline phase may be important for a better understanding of both pesting and the protection mechanism. Therefore, since the only available general description of the pest phenomenon was that of Fitzer, it was decided to reproduce his experiments. These experiments established that, in addition to the "pest" and "nonpest" temperature range, an intermediate region exists between 600" and approximately 650°C. This region is characterized by the appearance of a variable amount of yellow to orange colored crystals. The electron-beam microanalyzer was used to qualitatively determine their composition. Iron and molybdenum were found to be major constituents. This result can be explained based on the following facts: 1) iron, according to literature data,* is the most common impurity in molybdenum powder, and its content can be as high as 0.25 pct; 2) technical silicon powder usually contains iron; 3) steel ball mills are often used for the crushing and grinding of MoSi2. In order to clarify the exact role of iron, it was deliberately added to a stoichiometric mixture of molybdenum and silicon. The observed results corroborated the previous experiment, proving that iron (probably as some silicide phase) concentrates along the grain boundaries. I) EXPERIMENTAL PROCEDURE A) Oxidation of MoSi2 with Iron Additions. 1) Specimen Preparation. Specimens were prepared by both

Jan 1, 1967

By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker&apos;s view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker&apos;s view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957