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By David Schlain

IN 1942 the Bureau of Mines began to develop the Kroll process for use in the large-scale production of titanium. Titanium and titanium alloys are now commercial metals. These metals are relatively expensive, but It is now evident that they will have important industrial uses and that in many instances these will be related to their remarkable corrosion resistance. This bulletin presents the known corrosion properties of titanium and its alloys in useful form. In marine environments titanium is highly resistant to corrosion and does not pit, or undergo crevice corrosion, stress corrosion, or corrosion fatigue. Titanium is also highly resistant in many salt solutions, including most chlorides. It is very resistant to corrosion in nitric acid solutions. It is also resistant to white fuming nitric acid. However, it may react violently with red fuming nitric acid. In phosphoric acid solutions titanium has rela¬tively good resistance to corrosion, but it has less resistance to sulfuric acid and still less to hydrochloric acid solutions. Titanium corrodes very rapidly in hydrofluoric acid Solutions. It is very resistant to corrosion in many organic chemicals. However, it has only moderate resistance to formic acid solutions and poor resistance inn oxalic acid solutions. Titanium does not corrode in dichloroaretic acid but, corrodes rapidly in 100 percent trichloroacetic acid at 100° C. Titanium is resistant to barium, calcium, magnesium, ammonium, and sodium hydroxides. Titanium is inert in wet chlorine, bromine, or iodine gases. However, in dry chlorine gas titanium reacts rapidly enough to ignite. It also reacts rapidly with dry bromine gas, but, it is resistant to dry iodine gas. When titanium is exposed to red fuming nitric acid solutions with high nitrogen dioxide content and low water content, it corrodes, undergoes stress-corrosion cracking, and becomes pyrophoric. This occurs more readily with some titanium alleys, such as titanium-8 percent manganese. A fresh titanium surface immersed in water or in an aqueous solution and in contact with an oxygen-rich atmosphere under sufficientt pressure is unstable and will ignite spontaneously. Inherently an active metal, titanium has a tendency to become less active in environments containing oxidizing agents such as air, oxygen, chlorine, or ferric, cupric, or platinic ions. Titanium is more noble than most structural metals in roost, environments and its excellent corrosion resistance is generally not, affected by contact with these metals. However, some of the other metals corrode faster because of contact with titanium. Titanium undergoes anodic polarization readily, so that even when it is the less noble member of a galvanic couple it may corrode less because of the contact. Titanium alloys often have corrosion properties and electrochemical characteristics similar to those of commercially pure titanium. Titanium alloys containing noble metals, zirconium, molybdenum, vanadium, tantalum, or copper sometimes have better corrosion resistance than pure titanium.

Jan 1, 1964

By G. T. Lapidus

One of Society’s major concerns with hydrometallurgical processing is the large amount of water that is quintessential to its nature. This is especially troubling in arid areas, where the population struggles to procure potable water for their daily needs. For that reason, it has become our responsibility to conceive, design and implement processing schemes that not only use as little water as possible, but recycle streams within the plant itself and minimize waste that exits its perimeter. With this in mind, the conference will center on the importance of selecting the appropriate chemical systems and integrating material balances to avoid reagent overkill and to detect impurity accumulation. The three “R’s” (reuse, recycle and recovery) of aqueous solutions within the processes are emphasized. Examples of processes for the recovery of lead, copper, precious and PG metals from minerals and waste materials will be presented.

By J. H. Holden

The Federal Bureau of Mines is doing research and development work on a pressure-gasification pilot plant for producing synthesis gas directly from pulverized coal, oxygen, and steam. A pressure-gasification pilot plant has been constructed, and an investigation was made with the following basic objectives: 1. Determining the effect of varying pressure (75, 100, 150, and 300 p.s.i.g.), coal rate (400, 700, and 1,000 pounds per hour), and oxygen-to-coal ratio (8 to 11 std, c,f. per pound), on percentage of carbon gasified, oxygen and coal requirements per unit of CO + H2 produced, exit-gas temperature, and heat loss. The steam-to-coal ratio was maintained at approximately 0.3 pound per pound. 2. Development of a stabilized gasification zone or reaction space. 3. Improvement in operability of the pilot plant.

Jan 1, 1960

By C. G. Bieber, R. F. Decker

The effects of minor constituents on the malleability of nickel alloys are described. These effects are related to the atomic diameter, valence, and position on the Periodic Table. The basic methods for removal or neutralization of deleterious elements are then reviewed. Finally, practical methods for melting nickel alloys are described in detail and related to minor constituent control. L HE first malleable nickel was produced by Fleit-man in about 1870 by the addition of manganese and magnesium to the molten metal to counteract the harmful effects of sulfur. Merica and Waltenbergl explained the mechanism by which these elements accomplished the desired result. They showed that sulfur in concentrations in excess of about 0.005 pct produced films of a brittle low melting eutectic of nickel-nickel sulfide which completely surrounded the grains. When manganese was added to molten nickel it reacted with the sulfur to form manganese sulfide which precipitated as widely scattered globules in the grain boundaries. The further addition of small amounts of magnesium converted the sulfur to a very stable sulfide of magnesium which was relatively insoluble in both the liauid and solid states and therefore occurred as finely divided particles within the grains where it had relatively little detrimental effect upon the malleability of nickel or its alloys. The practice of treating nickel with manganese and magnesium came to be called "deoxidation" and was employed without appreciable modification for the commercial production of wrought nickel and high nickel alloys (in this paper—50 pct or more nickel) until about 1930 even though the results were never entirely satisfactory. At that time a more extensive study was made of the effects of minor constituents on malleability and metallurgical quality. The results, small portions of which have been published,2-4 are presented here with other pertinent data. EFFECTS OF MINOR CONSTITUENTS UPON NICKEL Systematic additions were made of 0.5 pct or less of each of most of the elements of the periodic ta- ble. It was established in this study that some minor constituents other than manganese and magnesium were extremely influential. The malleability, as evaluated by the reduction of area in tension tests, depended roughly on temperature as shown in Fig. 1. Four temperature zones are of interest; the cold malleable zone (up to about 1000° F), the red short zone from roughly 1000° to 1500' F, the hot malleable zone around 2000° F and the incipient melting zone. Most of the malleability problems are associated with the red short zone and the discussion will concern this mainly. The reduction of area in normal tensile tests on high-purity nickel (see curve A of Fig. 1) appeared to have no

Jan 1, 1962

By William T. Folwell

The Lucky Friday mine east of Mullan, Idaho, is an outstanding example of a property in the Coeur dlAlene district where a small and insignificant-appearing silver-lead-zinc vein at the surface has changed at depth into a large vein of great importance. The Lucky Friday vein has little if any surface expression and above the 1200 level the ore shoots are small and discontinuous. Between the 1200 level and 2450 level, the lowest developed level, the main ore shoot has shown remarkable improvement on each succeeding lower level, and today the mine is one of the major lead-silver producers in the Coeur d'Alene district. History: The Lucky Friday property is on the north side of the South Fork of the Coeur d'Alene River in sections 25, 26 and 35, T. 48 N., R. 5 E., Hunter mining district, Shoshone County, Idaho. This is about one mile east of the town of Mullan, which serves the eastern portion of the Coeur d'Alene district. The southern part of the property is crossed by a branch line of the Northern Pacific Ry. and by U. S. Highway 10. This highway is the principal road crossing the panhandle of Idaho and connects the district with Spokane, Wash., on the west and Missoula, Mont., on the east. The main portal and surface plant of the Lucky Friday mine is at an elevation of 3365 ft, only a short distance above the valley floor and a few hundred feet from U. S. Highway 10. so the mine is readily accessible for year-round operation. The property is comprised of six claims, known as the Lucky Friday group, owned outright by the Lucky Friday Silver-Lead Mines Co. There are four patented claims, Good Friday, Lucky Friday, Northern Light, and Lucky Friday Fraction No. 2 (Mineral Survey No. 3028), and two unpatented claims, Hunter and Creek. In addition, Lucky Friday owns an undivided one-half interest in the Hunter Creek property. which adjoins the Lucky Friday group on the north: a 90 pct interest in the mineral rights in the Jutila Ranch (160A), which adjoins the Lucky Friday group on the east; and a 60 pct interest in the Lucky Friday Extension claim group, which adjoins the Lucky Friday group on the west. The company also has a long-term mining lease on the Hunter Ranch, which adjoins the Lucky Friday group on the west. The claims of the Lucky Friday group were located between 1899 and 1906. The Lucky Friday Mines Co. was organized in 1906 and did considerable exploration work by surface trenching and shallow underground workings, only to see the property sold by the Shoshone county sheriff to satisfy labor claims totaling $2000 in 1912. Another firm, Lucky Friday Mining Co., bought the claims in 1914 and spent 12 years driving what is now known as the tunnel level crosscut. This tunnel intersected a vein previously exposed in a higher tunnel, but it was only a few inches wide. The vein was followed a short distance westerly but was so unpromising that the work was discontinued in favor of extending the main crosscut tunnel several hundred feet north. No ore was found and all work was discontinued. The property was held in such low esteem by the firm that it let taxes amounting to less than $15 a year go delinquent for nine years. Then the property lay idle for two more years until in 1938 John Sekulic, a Mullan service station operator, took a lease, with a $15,000 purchase option, on the advice of an old miner who had worked in the mine. Sekulic re-opened the tunnel level crosscut and explored the vein with an easterly drift for about 200 ft. The vein was too narrow to be of commercial value but was believed interesting enough to warrant further exploration at depth. Lacking funds to explore the vein at depth, Sekulic tried to get the district's larger operating companies to take over his lease and option. They were not interested because of the lean tunnel level showing and the fact that the property lay between the White Ledge fault on the north and Osburn fault on the south, an area which geologists always considered unworthy of exploration. Sekulic then organized the present company and assigned his lease and option to it for stock. This was in 1939. Enough stock was sold locally to finance sinking of a shaft 100 ft from the tunnel level east drift. The vein at this additional depth still was not commercial but showed some improvement. Treasury stock was offered at 5 to 10C a share

Jan 1, 1959

By E. J. Matson

Under the investigation for critical and strategic minerals the Kaiser mine, formerly the Baxter fluorspar property, in northeastern Mineral County, Nev., was explored. The work comprised excavating 32 trenches averaging 90 feet in length, 8 feet in width, and 1 1/2 feet in depth. The trenches were excavated across the strike of the ore body to enable the engineer to spot the diamond-drill holes; 7 such holes were drilled, aggregating 3,276 linear feet. A total of 20 core samples and 107 sludge samples was taken. The work under this program indicated that the fluorspar southwest of the deposit extended laterally and also at depth at least 250 feet below the 400-foot level. INTRODUCTION The Kaiser fluorspar deposit is in the northeastern portion of Mineral County, Nev. Mining was begun about 1928, and the property has been a consistent producer of both Acid- and Metallurgical-grade fluorspar. The mineralized zone has been developed along a strike length of about 2,000 feet and to a depth of over 700 feet along the dip.

Jan 1, 1957

By W. S. Landers

This report presents a study by the Federal Bureau of Mines of technical factors related to the production of special carbon and tar from selected Wyoming coals. Certain Wyoming high-volatile bituminous and subbituminous coals were processed in bench-scale apparatus to determine potential carbonization yields and in pilot plant retorts to produce sufficient char and tar for testing. These tests have shown that a critical selection of coal is necessary when the coal is processed for a specialized carbon. Generally high yields of tar are obtained from low-temperature carbonization of Wyoming high-volatile bituminous and subbituminous coals, and the yield of tar usually increases with increase in rank within this range of coals. The production and evaluation of industrial carbons from Wyoming coals by using pilot plant and bench-scale techniques is part of the continuous program of upgrading western coals. It has been found that: 1. Most Wyoming coals are nonagglomerating and may be carbonized in fluidized systems. Chars produced in pilot plant retorts at low temperatures contain about 17 to 23 pct, residual volatile matter and are easily ignited. These chars appear suitable as power plant fuel. The tar-plus-light-oil yields range from 14 to 40 gal./ton of raw coal processed. 2. Wyoming high-volatile coals produce a slightly smaller and somewhat weaker coke than currently mined Western United States high-volatile coals used commercially as blending stock in metallurgical coke production.

Jan 1, 1961

By E. J. Murphy, A. P. Rowles, John C. Holtz

"INTRODUCTION The use of sheaths or hollow cylinders of flame-extinctive materials surrounding cartridges of permissible explosives has been developed during the last few years; the history of sheathed explosives in their salient development in Belgium was treated recently in a publication of the Bureau of Mines. 6/ This development is of great interest in explosives technology, for it holds possibilities of reducing further the ignition hazards that may cause many coal-mine disasters. The township interest in sheathed explosives in this country is attested by the passage of some State laws permitting the use of such explosives on shift 7/; inquiries are received in increasing numbers concerning the effects of sheaths on practical hazards as well as the general technology underlying their use."

May 1, 1943

By [F. P. ] Stambaugh

Results of research on the hydrothermal precipitation of zirconium oxide from the Bureau of Mines' zirconyl chloride-sulfate strip liquors indicate that nuclear grade material can be prepared by this process. Greater than 99% of the zirconium value can be precipitated at 250-260°C in short (5-10 minutes) reaction time without consumption of acid value of the liquor. Thus, precipitation of zirconium dioxide on a continuous basis, i.e., the zirconium dioxide is precipitated in a continuous mode of operation by pumping the strip liquor through a heated pressurized reactor and recycle of the acidic (spent) liquor to the process stage are favored. The results of accompanying studies of liquod/solid separation, product washing and dewatering, product purity, and chlorination of the product are presented and discussed.

Jan 1, 1980

Production implications of the introduct- ion of electric L.H.D. units in sublevel open stoping and pillar recovery at Rosebery are covered by Faulkner (1982) and Carlton (1982). The following engineering aspects associated with the decision to introduce electric L.H.D.'s are considered here: - Initial requirements for commissioning, including power reticulation at an adequate level to all operating areas. - Conversion of a manual system to radio remote control. - Maintenance backup requirement to ensure that the production potential is realised.

Jan 1, 1982

By Donald Koch

The project investigated regional impacts of mining on the ground water system of the Powder River Basin by: 1) establishment of a regional ground water monitoring network, and 2)development of , set of digital computer models to simulate ground water flow and quality, ground water contributions to surface water flow and quality (i.e., baseflow), and watershed run-off and recharge. Over 100 wells were monitored for physical and chemical parameters. Data were used as input to the model; and for the development of a comprehensive data base. The basin was modeled on a regional and subregional scale using a finite -difference model employing an alternating difference technique. Two water-shed models were evaluated for their ability to provide runoff and recharge inputs to the basic ground water model. Application of the regional and subregional models using conservative mining scenarios showed that drawdowns may extend west from the mines as far as ten miles but that impacts would be insignificant on a regional scale. The watershed model could be effectively applied to small watersheds only.

Jan 1, 1982

CONTENTSThe significance of values givenINTRODUCTIONTHE ORE1. DATA SECURED FROM THE MILLING PLANT AS OPERATING BETWEEN 1938 AND 1942(a) Mill Recoveries(b) Mill Flow Sheet(c) Scheelite-Garnet Association(d) Detailed Examination of Mill Performance during 1942Crushing UnitsCoarse Rolls DischargeFine Rolls DischargeFeed to Huntington MillsFinal Ground ProductProduction of -200-mesh Scheelite SlimeSummary of Information on Crushing and Grinding Circuit(e) Detailed Examination of Mill Performance During 1942Concentrating UnitsLocation and Nature of Scheelite LossesSize Distribution of Scheelite LossesDistributor Spigot ProductsSummary of Information on Concentration Circuit(f) Detailed Examination of Mill Performance During 1942 Gravity Plant Feed2. EXAMINATION OF MINE SAMPLES TAKEN DURING 1942(a) Introduction(b) Nature of the Ore(c) Sampling of Mill Feed(d) Testing Technique(e) Minus 1/8-inch Ores-Naturally Broken Fractions(f) Recoveries from Plus 1/8-inch Fractions-Crushed to Minus 1/8-lnch(g) Probable Recoveries Obtainable from Weathered Ores140 Contour120 Contour90 Contour(h) Examination of an Ore Sample from the 90-foot Adit(i) Run-of-Mine Ore(j) Evidence of Maximum Sizes of Scheelfte Present in Run-of- Mine Ore(k) Summary of Information on Liberation and Recovery from the Ores as Mined in 1942 and from the Mill Samples

Jan 1, 1944

By P. J. Sylvester, D. H. C. Wilton, R. I. Wheeler, M. A. E. Huminick, D. Evans-Lamswood

"Abstract — Systematic characterization of the mineralogy of massive sulfide ore deposits can provide valuable insights into ore genesis and metallurgical processing that would not be apparent otherwise. We describe a method wherein (1) normative mineral abundances are calculated from whole-rock chemical assays using an algorithm, (2) the results are cast in block models, (3) the results are then verified with automated image analysis of a subset of samples prepared as grain mounts by backscattered electron imaging and X-ray mapping on a scanning electron microscope, and (4) those verified results are integrated with textural data determined by optical microscopy.The technique is applied to the magmatic Ni-Cu-Co sulfides of the Ovoid orebody, based on geochemical assays of 3175 whole-rock samples. Three principal ore zones are defined in the Ovoid. Type I ore occurs in the center of the deposit; it is magnetite-rich and pyrrhotite-poor with intermediate contents of pentlandite and chalcopyrite. Type II ore surrounds Type I ore and is pentlanditechalcopyrite- rich with intermediate contents of pyrrhotite and magnetite. Type III ore occurs at the base and along the outer periphery of the northern part of the orebody; it is pyrrhotite-rich and chalcopyrite- poor with an intermediate content of pentlandite, and a low-to-intermediate content of magnetite."

Jan 1, 2012

By C. C. Popoff

The Dunkleberg district is in the Flint Creek Range of the northern Rocky Mountains, about 45 miles northwest of Butte, Mont. Silver - lead and zinc mineralization occurs over an area 4 miles long from north to south and 1 to 2 miles wide from west to east. Ore in appreciable quantity has been produced, mostly from the Forest Rose group of mines in the southern part of the district. The Forest Rose mine was the largest producer of lead and the Wasa mine, a mile farther south, the main producer of zinc. The total output of ore from these properties during World War II was 113,000 tons, or 98.2 percent of the total recorded production of the district. The Wasa mine was examined by a Bureau of Mines engineer2/ in 1944. Subsequent investigations during 1946, 1947, and 1948 included trenching and drilling Fn the Wasa area and examination of the Forest Rose and other mines.

Jan 1, 1953

By C. C. Popoff

This report reviews the phosphate deposits, mines, and industry, and prospects in 10 districts covering most of the Montana phosphate field. These districts are discussed individually, and an evaluation of the resources and potential of each is presented. Phosphate rock produced from underground mines in the Garrison district is shipped to Canada for processing to fertilizers, utilized locally for production of animal feed supplement, and pulverized and sold for direct application to the soil. Production from the Melrose district is shipped to Silver Bow and processed to elemental phosphorus. The Maxville-Philipsburg district is destined to become a major producer with the development of the Douglas Creek mine and beneficiation plant by Montana Phosphate Products Co. Montana ranks fourth after Florida, Tennessee, and Idaho in total annual production in the United States. Production him increased from about 60,000 long tons of acid-grade phosphate rock in 1940 to more than 660,000 tons of acid-, beneficiation-, and furnace-grade ore in 1961. Montana has the second largest potential resources in the Western field; in the area south of Butte there are approximately 1.2 billion tons of phosphate rock (+18 to +31 pct P2O5) available above and within 100 feet below entry level; and in the northern part of the field there are about 67.6 million tons available above entry level. In contrast to Idaho, most of the phosphate deposits in Montana are best suited to underground mining.

Jan 1, 1965

By K. J. Ladwig

The Bureau of Mines conducted a field investigation of the water quality in inundated underground coal mines in the Northern Anthracite Field, eastern Pennsylvania. Water samples were collected at multiple depths from nine abandoned mine shafts in the Wyoming Basin, ranging from 68 to 650 m (223 to 2,132 ft) in depth and intersecting as many as seven mined seams in a single shaft. The shafts were also monitored for fluid resistivity, fluid temperature, Eh, and pH using downhole instrumentation. The monitoring program showed that the formerly highly acidic mine water is now slightly alkaline. Sulfate concentrations decreased as much as 74 pct in the flooded workings and 54 pct at a mine water discharge from values reported in 1964 and 1968, respectively. These data are consistent with the inhibition of pyrite oxidation and gradual flushing of oxidation products in flooded mine environments. The monitoring program also revealed significant vertical stratification in water quality in five of the nine shafts, each characterized by two easily recognizable zones. The transitions between zones were sharp, marked by rapid changes in Eh, pH, and ionic composition, the upper zones being less contaminated than the lower zones. The development of stratification appears to be a function of shallow localized flow conditions, arising primarily from the relative positions of mine openings and structural features of the coalbeds.

Jan 1, 1984

By H. E. Rorschach

Activity in Oklahoma fields declined in 1938 from the banner year of 1937. During the year, 1768 wells were completed as compared to 2632 completed during the year 1937. The following tabulation sets out details regarding the wells completed during the year: These computations do not take into account the wells drilled for repres-sure and salt-water disposal, and other nonexploratory wells. Purchasers' reports filed with the Corporation Commission of the State of Oklahoma show a total of 168,789,229 bbl. of oil purchased from Oklahoma leases in 1938, or a daily average of 462,436, a decrease of about 25 per cent from the year 1937. The outstanding operation of the year was the further development of the Ramsey pool, in western Payne County, the producing horizon being classified as the Wilcox. This pool was discovered on the last day in the year 1937, by the Mid-Continent Petroleum Corporation drilling on a unitized block in see. 18, T. 18 N., R. 2 E. The map in Fig. 1 shows the development at the end of the year 1938. An important discovery of the year was the Champlin Refining Company's No. 1 Boehm, in Garfield County, sec. 4-24N-8W., the producing horizon being the second Wilcox found at a depth of approximately 6700 ft. This pool was assigned the name of Hillsdale. Some of the offsets to this discovery well had not come up to expectations at the end of the year, but the discovery seems to be important as indicating that the Wilcox sand is productive in the Anadarko Basin area, providing that the right structural conditions are present.

Jan 1, 1939

By H. E. Rorschach

Activity in Oklahoma fields declined in 1938 from the banner year of 1937. During the year, 1768 wells were completed as compared to 2632 completed during the year 1937. The following tabulation sets out details regarding the wells completed during the year: These computations do not take into account the wells drilled for repres-sure and salt-water disposal, and other nonexploratory wells. Purchasers' reports filed with the Corporation Commission of the State of Oklahoma show a total of 168,789,229 bbl. of oil purchased from Oklahoma leases in 1938, or a daily average of 462,436, a decrease of about 25 per cent from the year 1937. The outstanding operation of the year was the further development of the Ramsey pool, in western Payne County, the producing horizon being classified as the Wilcox. This pool was discovered on the last day in the year 1937, by the Mid-Continent Petroleum Corporation drilling on a unitized block in see. 18, T. 18 N., R. 2 E. The map in Fig. 1 shows the development at the end of the year 1938. An important discovery of the year was the Champlin Refining Company's No. 1 Boehm, in Garfield County, sec. 4-24N-8W., the producing horizon being the second Wilcox found at a depth of approximately 6700 ft. This pool was assigned the name of Hillsdale. Some of the offsets to this discovery well had not come up to expectations at the end of the year, but the discovery seems to be important as indicating that the Wilcox sand is productive in the Anadarko Basin area, providing that the right structural conditions are present.

Jan 1, 1939

By P. Chiotti, G. R. Kilp

Thermal, metallographic, vapor pressure, and X-ray data were obtained to establish the phase diagram for the zinc-zzrconiz~m system. Five compounds corresponding to the stoi-chiometric formulas ZrZn, ZrZn,, ZrZn,, ZrZn,, and ZrZn14 were observed. All these compounds, with the exception of ZrZn2, which melts congruently at 1180°C under constrained zinc-vapor conditions, undergo pexitectic reactians. The temperature at which the zinc vapor pressure is I atm for a series of alloys was determined from vapor-pressure measurements. The data obtained are summarized in the construction of a I-atm-pressure phase diagram and a phase diagram corresponding to a pressure of less than 10 atm. THE purpose of this investigation was to establish the phase diagram for the zinc-zirconium system. Thermal, metallographic, vapor pressure, and X-ray data were employed in determining the phase regions. Partial investigations of this system have been conducted by Gebhardt1 and Carlson and Borders.' Carlson and Borders studied the high-zirconium region and established the existence of a eutectic at 69 wt pct Zr with a melting point of 1015°C. The terminal phases of the eutectic horizontal were shown to be an intermetallic compound ZrZn and a solid solution of ß zirconium containing 21 wt pct Zn. The ß solid solution decomposes into ZrZn and a zirconium at 750°C. The eutectoid composition is given as 15 wt pct Zn, and the solubility of zinc in a zirconium at temperatures below 750°C is indicated to be negligible. Gebhardt studied the zinc-rich region and observed a lowering of the melting point of zinc from 419.5" to 416°C and temperature horizontals at 545" and970°C. Some preliminary observations by Chiotti, Ratliff, and Kilp were reported by Hayes.2 pietrokowsky3 has reported the compound ZrZn2 to have a cubic MgCu2 structure with ao = 7.396A. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc or Baker analyzed reagent granulated zinc, both 99.99 pct pure and hafnium-free iodide-process crystal bar zirconium obtained from the Westinghouse Electric Corp. The zirconium contained 200 ppm Fe, 200 ppm Si, 100 ppm C, and minor amounts of other impurities. The zirconium was milled or machined into thin chips or shavings. These were cleaned with a nitric-hydrofluoric acid solution, rinsed with water, and acetone, and dried just prior to their use in alloy preparation. The granulated zinc was similarly cleaned using dilute nitric or hydrochloric acid. Weighed quantities of these materials, 20 to 30 g total, were mixed and pressed at 20,000 to 70,000 psi to give relatively dense compacts. During the early part of this investigation the pressed compacts were placed in MgO-15 wt pct MgF, crucibles which were then sealed inside of quartz ampules. The compacts were given various prolonged heat treatments prior to their use for thermal analyses, or vapor-pressure measurements. Because of expansion of the compacts and the relatively high zinc vapor pressure it was difficult to heat to the melting temperatures of the alloys without failure of the quartz ampules. Homogenization at temperatures below the melting temperature gave brittle, porous alloys unsuitable for metallographic examination. It was also difficult to prevent condensation and segregation of zinc on the colder parts of the quartz ampules during heating and cooling operations. These problems were eliminated to a great extent by the use of tantalum crucibles. Tantalum proved to be a satisfactory container with little or no reaction between the alloys and the tantalum. Small tantalum thermocouple wells were successfully welded in the bottom of these crucibles. Pressed compacts were sealed inside the tantalum crucibles by welding on preformed caps under an argon atmosphere. Heat treating and differential thermal analysis were combined into a single operation. The experimental sample assembly is shown in Fig. 1. This assembly was enclosed inside a stainless-steel tube heating chamber which could be evacuated and filled with an inert gas. The thermocouple leads were brought out of the heating chamber between two rubber gaskets used to provide a vacuum seal for the water-cooled head. Most of the compounds in this system undergo peritectic decomposition. After heating above the temperature of a particular peritectic horizontal the sample was cooled to just below the peritectic temperature and held at temperature for several hours. The sample was then reheated through the peritectic temperature and the size of the thermal arrest, if still present, compared with the one previously obtained. If the thermal arrest was not characteristic for the alloy composition being investigated its magnitude diminished and repeated cycling and annealing eventually eliminated it. The peritectic thermal arrests characteristic of a particular composition were established in this manner.

Jan 1, 1960

By H. B. Jensen

STUDY of the thermal-solution process was begun by treating crushed oil shale in a small autoclave at temperatures of 700° to 950° F. The effect of temperature, reaction time, type of solvent, and richness of shale upon the amount of organic matter that was removed from the oil shale was thus determined. Following this orientation work a semicontinuous, bench-scale apparatus was built so that heated solvent could be pumped through a bed of shale under elevated pressure, thus removing the converted organic matter from the spent shale. After some operating experience had been gained, a continuous unit was constructed. This permitted treating a slurry of shale oil and pulverized oil shale at about 300 p. s. i. and temperatures of 750° to 850° F. for various retention times. Considerable cracking and polymerization of the shale oil were found to take place during the process. In an attempt to prevent this, a study was made of extraction of the shale in batch-type autoclaves under high partial pressures of hydrogen at total gas pressures of as much as 4,300 p. s. i. at 850° F. The thermal-solution process was found to convert over 90 percent of the organic matter in oil shale to oil and gas. The highest yields of gas and oil obtained without hydrogen pressure were equivalent to 119 weight-percent of those obtained from the same shale by Fischer assay. With a high partial pressure of hydrogen, yields equivalent to 126 weight-percent of Fischer assay were obtained. However, the oil produced by thermal solution has a higher boiling range than that obtained by other retorting methods, particularly so if the thermal-solution process is used without a high partial pressure of hydrogen. Nondistillable oil (all benzene-soluble material that would not distill under 2 mm. Hg absolute pressure without cracking) equivalent to over 100 percent of the organic matter in the shale was obtained without hydrogen pressure in the system. When the process was carried out under hydrogen pressure, the yield of nondistillable oil amounted to 60 to 70 weight-percent of the organic matter. Part of this heavy material is formed partly by polymerization and condensation of the shale-oil solvent used. These reactions, as well as cracking of the solvent to form gas and a carbonaceous deposit on the shale, are unfavorable features of the process.

Jan 1, 1953