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By O. S. North

As recently as the late 1920's there Were few indications that a 15-million-dollar-a-year industry would ever grow out of the mineralogic curiosity vermiculite. Today, it is an important industrial commodity, used primarily as an insulating material and lightweight aggregate, but with a wide range of other applications. The quantity of crude vermiculite produced and used in the United States increased 14-fold in the 17 years between 1935 and 1951. The vermiculite minerals are of secondary origin, formed by hydrothermal alteration of an ultrabasic igneous rock, generally pyroxenite, or by alteration of phlogopite or biotite mica or possibly other similar minerals. According to different authorities, vermiculite may originate either by direct hydrothermel means, by the weathering of biotite or phlogopite, or by a combination of these two agencies. Vermiculites frequently occur at or near the contacts of an acid intrusive rock, especially a pegmatite dike, with a basic or ultrabasic country rock.

Jan 1, 1953

By Ruddle R. W.

An outline account is given of the smelting of copper and the chemistry of the process. A table provides compositions of the more important minerals from which copper is won by smelting. Roasting is discussed as is smelting using reverberatory furnaces, blast furnaces and flash smelting. A brief discussion of converting covers the upright (Great Falls) converter and the horizontal (Peirce-Smith) converter.

Jan 1, 1953

"THE CONCEPT of energy as a commodity, while not entirely new, is not as widespread as the importance of the idea to this modern world would lead one to expect. The growth in the supply and use of energy over the past years has been tremendous, but our very closeness and familiarity have somewhat distorted the viewpoint, particularly of the younger generation. To many of us who remember the wonderful satisfaction of our first responsibility for directing two horsepower hitched to a farm cart or hay wagon, there still arises a feeling of some awe at the casual flick of the switch with which our sons and daughters summon to their convenience the service of some one hundred or more horsepower.Energy is the vital component of our existence and, no matter what contempt our day-to-day familiarity may •breed, it is wise to .pause from time to time and consider our national energy standing. Have we still capital in the bank? Are our expenditures wisely •conceived and well directed? Is provision being made for the years •ahead for the needs of our children and our children's children?"

Jan 1, 1953

By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO,, oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO, can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1M4 per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past y6ar that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ton of high-grade pyrite and results in 1/2 ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15d per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1953

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Paul W. Richardson

"Introduction And AcknowledgmentsTHIS PAPER outlines the geology and discusses the geological problems of the Mindamar mine. It is impossible to acknowledge the contributions of ideas of all the geologists who have worked in the area. Among the more important contributors are K. DeP. Watson, W. S. James, B.S.W. Buffam, and L. J. Weeks, and John MacPherson, the resident geologist at the mine.A mineralogical and chemical study of the ore and country rock is being carried •on by Dr. Watson at the University of California, Los Angeles.General InformationThe Mindamar mine is on Cape Breton Island, forty miles south-west of Sydney (Figure 1). The nearest railway stations are at St. Peters, which is thirty-two miles southwest of the mine, and at Sydney. Good gravel-surfaced roads connect the mine to the railways.The mine is producing at the rate of 600 tons a day of ore containing zinc, lead, copper, and minor amounts of silver and gold. At the present time the mill feed averages 9 .per cent combined metals, of which zinc makes u:p 7 1per cent and lead and copper each 1 per cent.General GeologyThe ore being mined ,by Mindamar occurs in a shear zone parallel to a northeasterly striking, vertically dipping, series of rocks consisting of rhyolite tuff, rhyolite, minor more basic flow rocks, and diorite (Figure 2). In the vicinity of the mine, these rocks have been termed the Mine Series. They belong to the Bourinot group, which has been assigned by L. J. Weeks to the Middle Cambrian. At the latitude of the mine, the Bourinot group is bounded on the northwest by the Stirling fault and extends eastward for two miles."

Jan 1, 1953

By Manuel Gomez

This report presents experimental work conducted on a number of coals found within the boundaries of the Missouri River Basin, which were, to an extent, a selection of coals typical of that region. In the min, the laboratory work falls into three general classifications: (1) Laboratory distillation assay of coal to establish yields on carbonization; (2) chemical analyses of the coal samples before drying or carbonization; and (3) chemical analyses of the products of carbonization. It will be seen in the following discussion that these data derived from the small-scale laboratory apparatus are useful in predicting yields from pilot plants or industrial units. Coal is produced in about 48 general areas or mining fields in the Western States, of which approximately 18 fall within the limits of the Missouri Basin.3/ Beginning with the Northern Colorado field, through the Central and Western Wyoming fields, the coal is principally bituminous and subbituminous rank. The western Montana coals are also of these ranks. Progressing northeast from central Wyoming the coal decreases in rank, as shown by the subbituminous C coals of the Gillette field in northern Wyoming and the lignites of eastern Montana and North Dakota.

Jan 1, 1953

By F. S. Crawford

This study was made to find methods of preventing back strains, among workers in brick plants, however, the information should apply to other industries that employ hand labor too process materials. The report is based on information in letters from. Bureau of Mines engineers and other safety men in the United States who visited numerous brick plants. Back strains, as wall as hernias and other muscular strains, result when certain body structures are subjected to strains greater than, they can withstand. Such breakdowns may be prevented simply by not straining these body structures. This is simple in theory but complicated in practice. It requires primary education of new workers and reeducation of older workers in the best method of lifting, preemployment physical. examinations to select employees for the jobs that require constant lifting, all possible mechanization of material-handling operations, relocation of machinery, and elevation of working surfaces to reduce to a minimum the muscular effort the workers must exert to perform operations impossible to mechanize. Accidents of any kind are a total bee for the American economy and decrease productivity; whereas mechanization raises the level of productivity and constitutes progress toward total safety. Heavy lifting should be done mechanically whenever possible, saving the men to direct the machines. This is an essential step in preventing strain accidents.

Jan 1, 1953

By Strathmore R. B. Cooke, Thomas E. Bam

The paper discusses the mineralogy, structure, and strength of magnetite pellets fired in air and in a neutral atmosphere at various temperatures. The information obtained from this investigation is used to explain the origin of the structures occurring in pellets produced by pilot-plant operation. MUCH experimental work has been performed on i-VL the mechanism of agglomeration and pelletiz-ing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiold and Ilmonil much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the micro-structures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.' Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl metha-crylate monomer." The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45"C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer's method.' Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of, these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wiistite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By Walter C, Smith

Metallic bismuth was known in the Middle Ages and the name is supposed to come from the German Wismut. The origin of the German name is uncertain. References to bismuth are found in the writings of Valentine, Paracelsus, and Agricola between 1450 and 1550. Early specimens of bismuth were very impure and often were confused with antimony, tin, and zinc. About the middle of the eighteenth century, J. H. Pott, C. J. Geoffroy, and Torbern Bergman succeeded in producing fairly pure bismuth and showed it to be an elementary metal similar in many respects to lead.

Jan 1, 1953

By L. L. Newman

PUBLIC UTILITY GAS PRODUCTION IN 1802, William Murdock first used retort coal gas to light his house and the Boulton and Watt plant where he was employed. For the next three quarters of a century coal served as the principal raw material for the manufacture of city gas for general distribution. Coal continued to hold its predominant position for another half century after Prof. Thaddeus C. Lowe developed the first practical method of enriching water gas with cracked-oil vapors in an integrated operation. This position, however, was no longer maintained through the medium of direct carbonization of coal in retorts but as a result of using anthracite or coke as the generator fuel in carburretted water-gas machines. The early water-gas machines were extremely crude and the consumption of both oil and generator fuel was very high. However, the cost of installation was considerably lower than for any coal-gas system having the equivalent gas-making capacity, the labor involved was small, and the water-gas machine could be started up and shut down quickly. It thus proved very useful as standby equipment and in taking peak loads from the coal-gas plants. The flexibility of the water-gas machine, furthermore, made it possible to change the candlepower of the gas readily to suit the required conditions. Later, when calorific value replaced candlepower as the standard of gas quality, the water-gas machine was found to be equally flexible in keeping the city gas under complete and convenient control. No basic improvements were made in the Lowe carburetted water-gas process until 1898, when means were added to provide for regular reversals of the flow of steam through the fuel bed. By judicious proportioning of the quantities of up-run and down-run steam, it became possible for the operator to control the hardness and position of the clinker to a degree that previously had been unattainable. Also in 1898, the first by-product coke plant in America to supply city gas was built at Everett, Massachusetts. Later many other by-product plants, of greatly improved design and capacity, were built, but not primarily for city-gas production, chiefly because of the relatively high investment cost per unit of gas made. Cheaper plant construction has been the subject of serious study, and some progress is expected, but other factors, such as plant life,

Jan 1, 1953

By J. B. Hess, C. S. Barrett

TO reach equilibrium between different phases in cobalt-rich alloys requires prohibitively long annealing cobalt-richalloystimes when temperatures are below about 700°C. The fact that a transformation from face-centered cubic to close-packed hexagonal readily tered takes place at temperatures below this in the cobalt-rich solid solutions is not an indication that thermally activated processes occur at an appreciable rate, for the transformation is well established as martensitic in nature. Wide divergence between heating and cooling experiments and high sensitivity to prior heat treatment make it difficult to judge temperatures of equilibrium between the phases.&apos; One object of the present work was to see if the information object of on the relative stability of phases could be gained by substituting plastic deformation for thermal agitation. Procedures were worked out that led to the determination of a diffusionless type of phase diagram, which represents the temperature of of phase equal stability for phases of the same composition, and the technique was applied to the Co-Ni system. Another object of the work was to see whether or not deformation would generate frequent stacking faults when these were thin lamellae of quentstackingfaultsa phase having higher free energy than the parent phase. The alloys were prepared in 80 to 100 g melts from cobalt (with metallic impurities estimated spectrochemically as follows: Ni, 0.05 pct; Fe, 0.001 pct.; Mg, Si, Cu, Cr, Al, < 0.001 pct) and Mond Car-bony1 nickel (with Fe, 0.05 pct; Si, 0.003 pct; C, 0.61 pct.; Cu, 0.001 pct; Co, Cr not detected, < 0.01 pct). The metals were melted in pure Al2O3 crucibles. An atmosphere of argon, that had been purified by passing over hot magnesium chips, was used for the alloys that, by analysis of the portions of the ingots actually used, were found to contain 15.3, 25.7, and 35.0 pct Ni, and vacuum melting (after degassing) was used for those containing 29.4 and 31.5 pct Ni. After induction melting the alloys were allowed to solidify in the crucible, and slices % in. thick x ½ in. in diam were annealed 12 hr at 1350°C for homogenization. These same specimens were used throughout the series of experiments, with annealing treatments of 4 hr at 900°C in purified hydrogen followed by furnace cooling, alternating with the deformation and X-ray tests discussed below. Results Spontaneous transformation was observed on cooling to room temperature in all alloys containing 29.4 pct Ni or less and by cooling the 31.5 pct alloy to — 195°C but was not observed in the 35 pct alloys after cooling to —195°C. These results are in satisfactory agreement with the cooling experiments of Masimoto.4 From these data it is clear that the temperature of beginning transformation M,,, drops to 20°C with the addition of about 30 pct Ni. The test for spontaneous transformation was metallographic. Specimens were thermally polished by annealing 10 hr in hydrogen at 1350°C, then furnace cooled; if trans- formation had occurred there were relief effects visible on the thermally polished surfaces. These markings were narrow straight lines, usually resolvable at high magnification as clusters of fine lines that resembled slip lines. It was concluded that they resulted from displacements on (111) planes, for the number of directions in individual grains often reached but never exceeded four, and lines could always be found parallel to the thermally etched (111) boundaries of annealing twins. The markings were thus consistent with the idea that the transformation occurs by (111) plane displacements (Shockley partial dislocations moving on (111) planes). This was further confirmed by X-ray tests for stacking disorders. Using an oscillating crystal technique previously employed to detect strain-induced faulting in Cu-Si alloys," streaks indicative of the stacking faults were looked for and found on X-ray films of the spontaneously transformed 25.7 pct Ni alloys, as expected by analogy with Edwards and Lipson&apos;s results on pure cobalt." The streaks were much intensified after rolling at room temperature. Transformation induced by plastic strain was investigated as a function of alloy composition and temperature of deformation. A series of tests was made to determine suitable straining and X-raying techniques. Filing was found inferior to abrasion in converting cubic samples to hexagonal, and abrasion was less effective than peening in producing smooth unspotty Debye rings in the X-ray patterns. Because the diffraction lines were broad, Geiger-counter spectrometer records of filings were less sensitive in revealing small amounts of transformed material than X-ray patterns recorded on films in a small diameter camera. After these exploratory tests the following methods were adopted. Specimens that had been annealed at least 4 hr at 900°C and furnace cooled were mounted in a block of aluminum, brought to temperature, and peened thoroughly with a mullite pestle preheated to the same temperature. The specimens were then quenched to room temperature. In peening, a circular area of % in. diam was given 500 blows. A few control tests showed that an additional 1000 blows did not detectably change the proportions of the phases present. The amount of transformation was judged by X-ray reflection patterns from the peened surface, using the innermost four lines of the cubic and the hexagonal patterns with filtered CoKa radiation,

Jan 1, 1953

By W. G. Bearden, P. P. Scott, G. C. Howard

This paper concerns the rupture or breakdown of rock formations as related to drilling, completing, and stimulating production of wells, and comprises data compiled from a study of literature and records of treatment of oil and gas wells. and from tests conducted in bores drilled into rock cores and outcrops of rock. Results of the investigation indicate that the internal pressure to rupture cylinders of rock and to breakdown rock formations surrounding a bore in the earth is dependent upon the extent of intrusion of fluids. the position of bedding planes. the ratio of internal to external diameter, the tensile strength of rock, and magnitude of confining pressure, and is independent of the size of bore, degree of fluid saturation. and temperature of rock within practical limits. It is concluded that the mathematical relationship of pressure in bores and stresses in the surrounding rock must not be limited by the simplifying assumptions of homogeneity. isotropy, and impermeability; that the incidence of lost circulation of drilling fluids to induced fractures may be reduced by preventing intrusion of fluids into the small intrinsic fractures along weak bedding planes; and that the magnitude of the breakdown pressure of wells to be treated may be lowered by removal of mud cake. INTRODUCTION The purpose of this paper is to present and discuss the results of tests which may serve to broaden the understanding of the phenomena of rupture or breakdown of rock and thus contribute to the improvement of the techniques for drilling and completing wells. including such operations as preventing lost circulation, stimulating production, and placing cement. Since the early recognition of the possibility of rupturing rock adjacent to a well by fluid pressure, the distribution and magnitude of stresses around a well and the internal pressure to cause failure have been expressed mathematically by application of the principles defining the elastic and inelastic behavior of thick-walled cylinders of a homogeneous. isotropic, impermeable material. In either the elastic or plastic state, if the conditions of homogeneity. isotropy, and impermeability were the normal characteristics of rock. there would be no reason to question the validity of the above principles when applied to rock. However. since most rock formations are characteristically permeable to some degree, contain bedding planes and small intrinsic fractures. and are heterogeneous, rendering invalid the assumptions of homogeneity, isotropy, and impermeability, the application of the thick-walled cylinder theories to the behavior of rock formations penetrated by a bore appears illogical. Also the failure to consider the effect of the properties of the drilling fluids, which certainly intrude in various degrees into most rock formations. is further cause for questioning the application of these principles. Even in the case of cylinders of hardened chrome-nickel steel, which would he considered relatively homogeneous isotropic. and impermeable, as compared to rock, it has been observed that the internal pressure capable of being withstood by the cylinders varied with the sizes of molecules comprising the rupturing fluid used. Because of these apparent weaknesses in the theories of the behavior of thick-walled cylinders when applied to bores in rock, and the importance of knowing the true behavior of rock under the influence of fluid pressure when planning drilling and completing procedures for wells, tests were undertaken to determine by observation the actual rupturing pressure of cylinders of rock and the effects of such variables as environmental conditions and characteristics of rock formations, fluid properties, and bore dimensions. It was intended that by these tests the validity of the thick-walled cylinder theories when applied to rock would be determined and, if found invalid, mathematical expressions would be derived for predicting stress and rupturing pressure of rock formations under various conditions. Since the derivation of mathematical expressions has been only partially completed, all of the results of the latter phase are not included in this paper. PROCEDURE The investigation was initialed with a study of the theories pertaining to the rupturing of thick-walled cylinders of homogeneous. isotropic, impermeable material and a study of the

Jan 1, 1953

By W. Rostoker

A STUDY of the titanium-oxygen system&apos; involved an associated series of measurements of the lattice parameters of the a and TiO phases. The results permit some interesting deductions which are herein reported. A comprehensive survey of the physical PI-operties of the phases in this alloy system has been made by Ehrlich.2 However, only impure titanium was available at that time, so that some revision of his measurements is to be expected. The lattice parameters were calculated from the high angle lines of Debye-Scherrer patterns taken in a 14 cm camera and using filtered CuKa radiation. The specimens were prepared largely by crushing and screening of lump samples which had been quenched from elevated temperatures. Only in the case of low oxygen contents was it necessary to resort to filing and annealing. The results of the lattice parameter studies are graphically presented in Figs. 1 and 2. It will be seen that oxygen produces a pronounced distortion of the c parameter of the a phase (hexagonal close-packed). The trend is in general agreement with Ehrlich&apos;s work, although the divergence of actual parameter values strongly suggests that his titanium was very impure. It will be noted that the a phase of titanium can tolerate the unusually high saturation solubility of about 34 atomic pct 0. By virtue of this unique effect, it is possible to make a calculation of the effective atomic diameter of oxygen when dissolved in a lattice with metallic bonding. This has not been possible before. Ehrlich&apos;s2 density measurements demonstrated that oxygen occupies interstitial positions in the a lattice and the trend of the lattice parameters would certainly support this. In a hexagonal close-packed unit cell the largest interstitial positions lie at (2/3, 1/3, 1/4) and (2/3, 1/3, 3/4). Accordingly, if both of these positions were occupied, the ratio of titanium to oxygen would be 1:1. The extrapolated c parameter may be taken as between 4.93 and 4.99?. The a parameter appears to reach a constant value of 2.955? at low oxygen contents. The distance of the center of a titanium atom site from the [vc2/16+a2/3-1.448] Then the atomic diameter of the oxygen atom is represented by the function: where the radius of the titanium atom is 1.448A,

Jan 1, 1953

By C. G. Dunn, M. Sharp

HE orientations of 137 crystals of copper pro-T duced by secondary recrystallization in a cube texture matrix have recently been obtained. Although the crystals were not prepared for the purpose of determining a secondary recrystallization texture, the orientations obtained proved to be rather interesting, as they confirmed, in part, published results and also disclosed additional preferred orientations in the texture. The investigation of Dahl and Pawlek,&apos; Bowles and Boas,&apos; and Kronberg and Wilson3 showed respectively that the orientations of secondary grains growing in a cube texture matrix were related to those of the primary grains by a rotation of approximately 30" about [001], the rolling direction, by 30" about a <111> direction, and by either 22" or 38" about a <111> direction. Kronberg and Wilson also obtained a component of the texture similar to that of Dahl and Pawlek except the angle of rotation about [001] was 19". When the cube texture matrix was deformed a small amount, Kronberg and Wilson also obtained large grains on subsequent annealing corresponding to a rotation of 15" about the normal to the sheet, but these grains should not be classified as secondary recrystallization grains since they were produced subsequent to mechanical straining. The particular texture obtained, of course, depends on the composition of the copper and the processing schedule employed, since these factors markedly affect the primary recrystallization texture and the sharpness of any cube texture produced. In the present investigation, pieces of OFHC copper in the form of M in. round bars were cold forged to a thickness of about 0.40 in., annealed 1 hr at 350°C in an atmosphere of hydrogen, and cold rolled crosswise to a thickness of 0.200 in. These pieces were given a penultimate anneal of 1 hr at 350°C in hydrogen and a 90 pct cold-rolling reduction lengthwise to a thickness of 0.020 in. Indentations generally were put in one end of the as-cold-rolled strips to promote earlier formation of secondary grains.

Jan 1, 1953

By J. G. Trowell, D. T. Magee

"IntroductionMANITOBA'S first recoverable oil was from the California Standard Daly 15-18 well in Lsd. 15, Sec. 18, Twp. 10, Range 27, W.P.M., completed early in 1951. This well also gave the first indications of commercial production in the Williston basin, which is centred in North Dakota and extends into southeastern Saskatchewan and southwestern Manitoba. Subsequent drilling in the Manitoba portion of the basin has revealed the presence of oil in more or less commercial quantities at various points in an area approximately four townships in width and eleven townships in length.Although completions are becoming fairlly widespread in the area,, the greatest activity is in the Virden district, with the focal point in the Daly field, approximately eight miles west •of Virden. This paper will deal with the various techniques used in the Daly field, where •completion problems have •been unusually troublesome. Techniques evolved there have already been used with success at other points in southwestern Manitoba.Daly FieldGeneralTo date, all production has been from the Mississippian limestone, which is encountered •at depths ranging from 2,300 to 2,500 feet. Pay thickness is •of the order of 100 feet. Core analyses indicate average porosity .of about 9 per cent but permeabilities, for the most part, are extremely low."

Jan 1, 1953

By E. E. Donath

THE coal hydrogenation process is well known as a means for production of liquid fuels from coal. In this paper, the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid-phase and vapor-phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high-molecular-weight aromatics and of tar acids and tar bases. The relative amounts of heavy and middle oil-boiling above and below 325ºC, for instance-can be influenced by temperature, residence time, and catalyst of the liquid-phase hydrogenation. In vapor-phase hydrogenation, a solid bed catalyst is used to convert the intermediate oil from the liquid-phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring-compound content of the liquid-phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparafhns.3 Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid-phase stage, coal is made into a paste with re- cycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high-pressure converters where the liquefaction of coal, conversion of the high-boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470ºC. The reaction products enter the hot catchpot in which oil vapors of lower boiling point

Jan 1, 1953

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

KNOWLEDGE of the isothermal transformation behavior and the TTT chart method of graphically summarizing such information has been of invaluable aid to the ferrous metallurgist in understanding and developing heat treatments intended to provide specific mechanical properties. It is to be expected that similar lines of study directed to titanium-base alloys will be as profitable. This paper summarizes, on conventional TTT charts, the isothermal transformation products and pertinent reaction rate data for binary alloys of titanium containing 1, 3, 5, 7, 9, and 11 pct Mo, respectively. The results so presented were derived from metal-lographic examination. Some X-ray diffraction work was done to clarify certain points of question. Ti-Mo System To the authors&apos; k.nowledge, TTT charts have only been used to describe the reaction rates of eutectoidal decompositions. It would seem that the kinetics of decomposition of any unstable solid solution might be conveniently described in this manner. The equilibrium diagram of the Ti-Mo system&apos; is shown in Fig. 1. The similarity with the Fe-Ni system will be recognized. Additions of molybdenum serve to stabilize the /3 phase to increasingly lower temperatures. The solubility of molybdenum in the a phase is restricted to less than 1 pct at 600°C. Under normal conditions. a homogeneous ,8 structure quenched to a, temperature in the a f & field will reject a of invariant composition. The rate at which this occurs depends on the degree of undercooling and the degree of supersaturation of /3. The structural character of the rejected phase may also be expected to be related to the undercooling. Materials and Experimental Methods A sponge titanium was used which has a nominal impurity content as reported in Table I. The nominal composition of the molybdenum used is also included. The alloys were prepared in 150 g melts by arc melting in an evacuated water-cooled copper crucible of the type reported in an earlier paper.&apos; The pancake-type ingots were forged to 1/4x1/4 in. bars and homogenized for 24 hr at 1000°C in evacuated Vycor bulbs. Specimens Vi in. thick were cut from these bars for heat treatment. The heat treatment cycles followed an invariant procedure. The specimens were soaked at 1000°C for 20 min under a helium protective atmosphere prior to quenching into a lead bath held at a temperature corresponding to a chosen degree of undercooling. After a prescribed period of time at this temperature, the specimen was removed and water quenched. A series of specimens so treated for progressively longer periods served to establish the times for initiation and completion of the decomposition of the /3 phase at a particular temperature. Although heat treatment of unprotected specimens in a lead bath does permit surface contamination by lead diffusion, this method is necessary to insure sufficiently rapid quenching rates. As long as the bath treatments were of less than 1 hr duration. the contaminated surface was not unduly deep and could be removed without excessive grinding. Metal-lographically, the contaminated zone could be readily distinguished from the pure binary alloy. Transformation Characteristics of Ti-Mo Alloys Metallographic examination showed that a supersaturated p phase may decompose by one of two processes. Alloys containing 1 to 9 pct Mo, when quenched in water from the homogeneous /3 field,

Jan 1, 1953

By J. A. Sutton

In connection with, a stream-pollution-research project, a colorimetric method was developed for concentrations of 1 to 30 p.p.m, of pine oil in water. The method depends on the stable bluish-green color produced when pine oil is reacted with vanillin-hydrochloric acid reagent at 60° C. for 25 minutes. The colorimetric reaction actually determines alphaterpineol, the principal component in pine oil. Some waters may require a special preparation in which ion-exchange resins are used to remove interference. ACKNOWLEDGEMENTS The author wishes to express his appreciation to A. A. Berk, chief of the Industrial Water Branch, Bureau of Mines, for helpful advice and encouragement during the progress of this work and to B. P. Martinez, chief of the Stream Pollution Research Section, for assistance with the manuscript. Thanks are also due to W. D. Bishop of the Hercules Powder Co., Wilmington, Del., for supplying the principal components of pine oil.

Jan 1, 1953