Search Documents

By Etienne A. Ritter

The Evergreen mine, located at Apex, in the northern part of Gilpin county, Colorado, has opened a very peculiar and interesting copper-deposit, in which both bornite and chalcopyrite occur as rock-minerals. The country-rocks are crystalline schists cut by dikes of granu-lite and of pegmatite. At the Evergreen property they have been cut by a dike of a uew kind of eruptive rock, to which I have given the name " Evergreenite." The rock is composed of quartz, alkali feldspars, orthoclase and albite (often interlocked as microperthite), with augite of the ægirine variety and long needles of enstatite and diallage. For reasons stated below, I believe the dike to be of Tertiary age. It is easily traced on the surface of the ground, from a point in the bottom of Pine creek, about a mile below Apex, to the top of Nevada hill, 1,500 ft. beyond and 600 ft. above it. (See Fig. 1.) It varies from 3 to 12 ft. in width, and is bounded on both sides by contact-zones about 60 ft. wide, in which the crystalline schists have been changed into pseudo-quartzites or pseudo-gneisees, according to the injection of an excess of quartz or of feldspars through the special layer of the schists. The most interesting feature is the presence of the pyroxenes, which are always found, though in very variable proportions from place to place, in the layers of these metamorphosed crystalline schists. The dike has torn from its walls a large number of fragments of the wall-rock. It must have been in a viscous state when that happened, because these fragments of the wall-rock do not show any sign of resorption or of assimilation by the magma. In places they are so distinct and so numerous that the rock looks to the naked eye like a pseudo-breccia, of which, never-

Jan 1, 1908

By E. Luttgen

The substance referred to in the title is the artificially prepared basic carbonate of magnesia, a compound of the carbonate with the hydroxide. It is the "block-magnesia " of commerce, the magnesia alba of the pharmacist. Its composition, though somewhat indefinite, may usually be expressed by the formula : 4MgCO3,Mg(OH)2, 5H2O; it is found to vary slightly with the details of the method of preparation. This substance has been employed recently with much reported success, as a non-conductor of heat. It is moulded to form coverings suitable for steam-pipes and their fittings and sectional jackets for boilers and cylinders; it is furnished also in forms suitable for lining refrigerators, walls and roofs of buildings, fire-proof safes, etc. It was with a view of ascertaining the efficiency of this material as a non-conductor, or, rather, its relative efficiency among the various non-conducting materials in use, that the writer made the experiments about to be described. A block of magnesium carbonate or magnesia alba exhibits some interesting physical qualities. It is a smooth, white, close-grained solid, in outward appearance resembling a block of Paris plaster. It possesses the lightness of cork, the porosity of sponge, and withal a degree of firmness and strength that, in view of its levity, is quite remarkable. To examine more closely the properties of this substance, a number of 1-inch cubes were sawed from the commercial block-carbonate, also some bricks, that is, blocks measuring accurately 2 x 4 x 8 inches, the dimensions of an ordinary brick. The cubes weighed from 2.2 to 2.7 grammes, the bricks weighed 140 to 175 grammes (5 to 6 ounces). The bricks were carefully measured and weighed, and placed in vessels containing distilled water, in which they became gradually submerged, owing to the displacement by water of the air inclosed in the structure of the magnesium carbonate. After twenty-four hours the blocks were removed from the water, dried superficially by contact with filter-paper and weighed. From the increase in weight, the volume of the water absorbed, and consequently that of the air displaced by it, were obtained. For example: a block which when dry weighed 155

Jan 1, 1887

By J. O. Betterton, W. M. Spicer

The solubilities of antimony in the a and ß-forms of zirconium were determined between 750" and 1300°C. The a-phase forms by a peritectoid reaction, and the a/(a + ß) and ß/(a + ß) phase boundaries rise in temperature with in- ' creasing antimony. Impurities in the 99.95 pct zirconium were sufficient to influence the phase boundaries and the variation reported is approximate. The restricted solid solubility of the terminal zirconium phases, which is especially characteristic of this system, is thought to result from the low free energy of the Zr2Sb phase. ZIRCONIUM-antimony alloys are important in zirconium alloying studies since antimony is one of the highest valent elements which can be used to make zirconium alloys. The dilute alloys are of further interest as they have somewhat better corrosion resistance' than pure zirconium. The first investigation of the phase diagram was made by Russi and wilhelm2 who found a eutectic reaction, liquid (- 17.5 at. pct Sb) = ß zirconium (- 11 at. pct Sb) + Zr2Sb, at 1430°C'. The Zr2Sb phase was of complicated hexagonal structure, and by thermal analyses of the relatively impure alloys then available, Russi and Wilhelm found evidence for the peritectoid formation of the a-phase. EXPERIMENTAL In the present work, the phase diagram was re-investigated in the region 0 to 5 at. pct Sb and 750" to 1300°C using iodide-zirconium alloys. Details of the procedure have been described earlier. Essentially the alloys were prepared by arc casting and were then examined by the annealing and quenching method. The times of annealing varied from 1 hr at 1300°C to 30 days at 760°C. As in other zirconium phase-diagram studies1"5 the impurities in the zirconium were still sufficient to affect the results, and the experiments will therefore be described in 3 parts. The results from the first 2 parts of the work are shown in Fig. 1. Here the ß/(ß + Zr2Sb) and a/(a + ZrzSb) phase boundaries were determined with alloys made from 99.9 pct zirconium,* and cast under such conditions that the Vickers hardness of a alloys extrapolated to 95 to 110 VPN at 0 at. pct Sb. Such alloys were not suitable for investigations of the (a + ß) region, and the results shown in Fig. 1 near the (a+ ß) and (a +ß + Zr2Sb) regions were determined with purer alloys. These alloys had an extrapolated hardness range of 75 to 85 VPN and were made from 99.95 pct zirconium. A deviation from binary equilibrium occurs in Fig. 1 as indicated by the (a + ß) region of pure

Jan 1, 1959

By M. E. Wadsworth

The chief value of a paper like this consists in its statistical tables, putting on record material useful to future inquirers. The data here given have been compiled from time to time as far back as 1874, and subsequently brought up to date. Much of the data could only be procured by personal inspection of the catalogues, as for example those relating to the Lawrence Scientific School, which were taken at that time from the catalogue of Harvard University, on file in the University Library, by the present writer, then an instructor in that institution. These tables of statistics were first prepared for publication by the present writer in 1888-1890 and published in his "Report to the Board of Control of the Michigan College of Mines " (Michigan Mining School) for 1886 to 1890. Later they were revised, enlarged and brought down to date in his reports to the same Board for 1890-92; and since that time they have been, at his request, revised, greatly enlarged and kept up to date by Mrs. Frances H. Scott, the efficient Librarian and Secretary of the Michigan College of Mines. Great credit is due to her for her devotion to this work and her untiring efforts to have the statistics complete as far as possible. The accompanying running commentary is given simply as a string to hold these statistics together, and in order to call attention to a few points. In compiling any tables like those accompanying this paper, one is confronted by serious difficulties, some of which render these results only approximate. In order to insure greater correctness and fullness in the statistics to be published the writer's reports for 1890-92 were sent to the president of every college, university, and technical school in the country, so far as known. Accompanying this was a personal letter which asked of each one his aid in correcting any errors, and in giving fuller statistics. But relatively few answers were obtained, and subsequently from one to many letters have been sent to each institution not formerly reply-

Jan 1, 1898

By J. D. Grace

Screening by centrifugal force is a unique subject, for all vibrating screens, with but one exception, depend on gravity alone to pass material through a sizing mesh or screen cloth. Centrifugal screening is one of the greatest advancements made in screening since the development of vibrating screens. It makes possible sizing in a range previously im-practical by mechanical methods. The centrifugal screen is specially designed for fine sizing from No. 4 separations to finer than No. 100 separations. Centrifugal force provides a positive control of factors that make fine particle separation practical and effective as opposed to gravity which is a fixed force acting only in a fixed direction, The centrifugal screen provides a control of the force of material against the screening surface, and also controls the distance of departure of the material from the surface and its rate of return. The centrifugal screen has a rotating drum that becomes a natural fan blowing air outward through the material being screened and carrying float dust and fines through the apertures with it. Screening by centrifugal force is an unique subject, for with the exception of only one vibrating screen presently on the market, all vibrating screens depend upon gravity to pass material through a sizing mesh or screen cloth. This one screen that sizes by centrifugal force and utilizes gravity only to convey material along the screen, is the Symons V-Screen. The requirements of the industrial minerals industry to meet ever-increasing stringent fine sizing specifications by a practical mechanical method accentuates the weakness of gravity, a fixed force acting in a fixed direction, as a prime force for fine sizing. It was apparent a force other than gravity was needed. This led to the development of a centrifugal screen to meet modern demands for practical fine sizing operations. Gyratory-type screens in use today were originally designed in a day when a 1/4-in. separation was normally considered fine sizing and 1/8-in. separations were extremely fine sizing. Although gyratory-type screens are sometimes used for separating below 1/8-in., they are not practical screens for this purpose. They were not designed to do this type of work. A growing demand for a practical means of making positive mechanical separations in a range of from 1/8 in. downward led to the development of the vibrating screen. These screens utilize higher speeds and lower amplitudes of vibration than

Jan 1, 1967

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By Roland Blanchard

Recent discovery at Mount Isa of copper mineralization in commercial amount at a depth of 1000 ft., coinciding with downward termination of ore at about the same depth within the larger silver-lead-zinc lenses that have been the standby of Mount Isa's production to date, has been cited as an example in support of mineral zoning. A previous paper by the author and Graham Hall1 furnished a detailed description of the geology of the ore at Mount Isa as exposed up to that time, but necessarily dealt mainly with the silver-lead-zinc mineralization. Most of the geologic facts that constitute the first half of the present paper were set forth in the previous one in much greater detail, with full supporting evidence for the facts cited. The large amount of underground development (approximately 20 miles) and the extensive exploration carried out by diamond drilling (100,000 ft.) at Mount Isa, added to extensive microscope work conducted over a period of years, both by the company's staff and by others, had made possible the calculation within fairly close limits of mineralogical composition of the principal mineralized block of ground down to 1000-ft. depth, and had established closely the mineral succession, with reasons for deposition of the various minerals in the patterns now occupied by them. The geologic facts as outlined in the previous paper remain as stated; but because substantial development within the new copper ore body and further exploratory diamond drilling within the new silver-lead-zinc area (Racecourse) have taken place since that paper was written, statements and figures relating to those two areas in the present paper supersede those furnished in the previous one. The recent work likewise has established more clearly the paragenetic relationship between the chalco-pyrite and galena. Evidence confirming the relationship is furnished in the present paper. The facts of ore occurrence at Mount Isa show Accepted Zonal Succession Silver sulphantimonides Galena Sphalerite Tetrahedrite Arsenical sulphides Chalcopyrite Pyrrhotite Mount Isa Succession I In the main but prob- Silver sulphantimonides ably not wholly Tetrahedrite I contemporaneous Galena Pyrrhotite Sphalerite Arsenical sulphides They show further: (I) that instead of the silver-lead minerals yielding to increased zinc in depth, the zinc yields to increased silver-lead; (2) no dovetailing of the silver-lead-zinc sulphides into chalcopyrite takes place; (3) despite the large amount of pyrrhotite deposited in the district (estimated at upward of 100,000,000 tons), its deposition took place under moderately low temperature conditions; (4) no evidence has been found for increase in temperature of deposition, with depth, to deepest exploration in ore (1475 ft.). The anomalous condition at Mount Jsa, both as to the unorthodox mineral succession and the largely unorthodox patteru of mineral distribution, is explained in the present paper,

Jan 1, 1949

By Roland Blanchard

Recent discovery at Mount Isa of copper mineralization in commercial amount at a depth of 1000 ft., coinciding with downward termination of ore at about the same depth within the larger silver-lead-zinc lenses that have been the standby of Mount Isa's production to date, has been cited as an example in support of mineral zoning. A previous paper by the author and Graham Hall1 furnished a detailed description of the geology of the ore at Mount Isa as exposed up to that time, but necessarily dealt mainly with the silver-lead-zinc mineralization. Most of the geologic facts that constitute the first half of the present paper were set forth in the previous one in much greater detail, with full supporting evidence for the facts cited. The large amount of underground development (approximately 20 miles) and the extensive exploration carried out by diamond drilling (100,000 ft.) at Mount Isa, added to extensive microscope work conducted over a period of years, both by the company's staff and by others, had made possible the calculation within fairly close limits of mineralogical composition of the principal mineralized block of ground down to 1000-ft. depth, and had established closely the mineral succession, with reasons for deposition of the various minerals in the patterns now occupied by them. The geologic facts as outlined in the previous paper remain as stated; but because substantial development within the new copper ore body and further exploratory diamond drilling within the new silver-lead-zinc area (Racecourse) have taken place since that paper was written, statements and figures relating to those two areas in the present paper supersede those furnished in the previous one. The recent work likewise has established more clearly the paragenetic relationship between the chalco-pyrite and galena. Evidence confirming the relationship is furnished in the present paper. The facts of ore occurrence at Mount Isa show Accepted Zonal Succession Silver sulphantimonides Galena Sphalerite Tetrahedrite Arsenical sulphides Chalcopyrite Pyrrhotite Mount Isa Succession I In the main but prob- Silver sulphantimonides ably not wholly Tetrahedrite I contemporaneous Galena Pyrrhotite Sphalerite Arsenical sulphides They show further: (I) that instead of the silver-lead minerals yielding to increased zinc in depth, the zinc yields to increased silver-lead; (2) no dovetailing of the silver-lead-zinc sulphides into chalcopyrite takes place; (3) despite the large amount of pyrrhotite deposited in the district (estimated at upward of 100,000,000 tons), its deposition took place under moderately low temperature conditions; (4) no evidence has been found for increase in temperature of deposition, with depth, to deepest exploration in ore (1475 ft.). The anomalous condition at Mount Jsa, both as to the unorthodox mineral succession and the largely unorthodox patteru of mineral distribution, is explained in the present paper,

Jan 1, 1949

By W. J. Joslin

The frontal-advance equation can determine how the fluid withdrawal rate and subsurface operating pressure influence oil recovery from pressure-maintained reservoirs having characteristics favorable for efficient vertical segregation. For effective vertical segregation in formations having low dip angles, the requirements are: thick, massive sands, low viscosity oil and high vertical permeability with few discontinuous shale members. This approach has been successfully applied to the LL-370, which is a massive Eocene sandstone reservoir containing crude with an average gravity of 26" APT, a dip of only 3" and vertical permeability of ½ darcy. The average gas cap saturation was calculated for various rates of vertical gas-oil contact movement corresponding to a wide range of reservoir producing rates. This method also evaluated the effect of different pressure maintenance levels on oil recovery. Applicability of this procedure for calculating the present oil saturation in the LL-370 gas cap has been substantiated from field performance, where the oil saturation was computed by comparing oil recovery with the gas cap volume vacated. INTRODUCTION During the natural depletion history of the LL-370 reservoir, located in Lake Maracaibo, Venezuela, excellent vertical segregation resulted in the formation of a thin gas zone over a substantial portion of the oil-productive area. Subsequently, gas injection forced this thin gas-saturated zone slowly downward, reducing the oil saturation in the gas cap to a low value. The oil recovery has been raised considerably above earlier predictions where vertical segregation effects were under-estimated. In order to determine the maximum efficient producing rate and optimum operating pressure for this reservoir, a vertical gas frontal-advance analysis has been made through application of the fractional flow equation. LL-370 RESERVOIR CHARACTERISTICS The reservoir consists of a truncated monocline of massive. highly-permeable Eocene sandstone, called the B-b formation, covering an area of more than 13,500 acres. The original oil in place was 2.17 billion STB. Internal non-sealing faults subdivide the structure into four blocks called the B-6-x.6, 10, 11 and 13, which are effectively bounded by major faulting on the flanks, an unconformity updip to the west, and an immobile aquifer to the southeast. The producing formation occurs at an average depth of 5,250 ft subsea and has a closure of more than 1,500 ft. A typical producing section has a net oil sand thickness of 170 ft. Scattered throughout the section are a few randomly-positioned shale lenses which increase in thickness and areal extent downdip. The reservoir rock and fluid properties vary with depth. The permeability and produced oil gravity are 1600 md and 28" API at the top, compared to 300 md and 18° API at the water-oil contact. The productivity of updip wells is, therefore, much higher than the reservoir average. The reservoir oil was originally saturated at the crest, grading to a slight degree of undersaturation at the water-oil contact. There was no original gas cap; and material balance and the field performance indicate no water influx. Except for the northern B-6-x.6 block, the fluid and rock properties have already been published.' Average LL-370 reservoir properties are shown in Table 1. RESERVOIR PERFORMANCE UNDER NATURAL DEPLETION Fig. 1 shows production performance from 1939 to date. Early development was gradual, with 30 wells pro-

Jan 1, 1965

By Frederic K. Bunton

The smelting plant of the British Columbia Copper Co. at Greenwood, B. C., now closed because of the decline in the price of copper due.to the European war, is of special interest to metallurgists for several reasons. It was successfully smelting in blast furnaces the lowest grade copper ore of all plants in America. In order to do so, it had to run at very hig~; efficiency, which necessarily required a large tonnage per square foot of hearth area, together with the minimum amount of labor and other costs. The furnaces smelted daily 2,250 tons of ore (6.62 tons per sq. ft. of hearth area), carrying 0.85 per cent. of copper, at a smelting cost of 81.18 per ton. The entire plant required 130 men to operate it and keep up repairs, showing a labor efficiency of about 17.5 Dons per man per day. In the present paper, the method of obtaining these results is shown. Most of the information contained in this description I obtained as Assistant Superintendent, during the two years preceding the present shutdown. Other sources of information to which I am indebted are: The British Columbia Copper Co., Ltd., by ALfred W. G. Wilson, in The Copper Smelting Industry of Canada; Greenwood Smelting Worlrs, by J. E. McAllister, Engineering and Mining Journal, vol. xci, pp. 1011 to 1015 (May 20, 1911); and Description of the Copper Smelter of The British Columbia Copper Co., by W. L. Bell, in Transactions of the Canadian Mining Institute, vol. xvi, pp. 151 to 154 (1913). II. Location and Connections The smelter of this company is about half a mile south of GreenGood, in the Boundary district of British Columbia, on the Columbia & Westerg branch of the Canadian Pacific Railway. It was originally built in 1900 by Paul Johnson, to handle 600 tons of ore a day in two small furnaces of 300 tons capacity; but in 1907 the old furnaces were torn out, the plant was remodeled, and three blast furnaces, 48 by 240 in. at) the tuyéres, were installed. In 1910, two of these were enlarged to 51 by

Jan 1, 1916

By M. S. Rashid, C. J. Altstetter

Allotropic transformations in cerium have been studied by dilatometric, resistometric, X-ray diffraction, and metallographic techniques. The dilatometric study indicated that, on cooling below O°C, the high-temperature fcc phase, y, transforms partly to the hexagonal phase, ß, and, on further cooling, to the collapsed fcc phase, a. The amount of $ phase present at room temperature is increased by repeated cycling through the a-y transformation. It has been shown metallograPhically that the y-ß transformation has many characteristics of a martensitic transformation. In contrast to the y-ß transformation the ?-a transformation does not give the manifestation of a shear transformation. Small cellular ? domains of random shape and size collapse to a in a short time with no apparent coordination with neighboring domains. The considerable confusion in the literature over the existence of more than one high-temperature fcc phase is discussed. Two such phases have been reported in the literature and an attempt is made in this study to clarify the situation. Twelve fcc and two hcp structures have been shown to be easily reproduced or eliminated. It is proposed that the two "additional" allotropes reported in the literature and fourteen of the phases detected here are not allotropes of cerium but are due to contamination. CERIUM exists in several allotropic forms, but there is some disagreement over what the forms are. Furthermore, the conditions favoring the presence of a particular allotrope and the nature of the transformations from one form to another are uncertain. The objectives of this research were 1) to ascertain the allotropic forms of cerium, 2) to establish the conditions under which the allotropes exist, 3) to study the effects of annealing and thermal cycling on the allotropic transformations, and 4) to study the transformation mechanisms. Dilatometric, resistometric, metallographic, and X-ray diffraction techniques were employed. The form of cerium commonly found at room temperature is fcc and is designated ?. A complex hexagonal phase, 8, forms when y is cooled to slightly below room temperature. At still lower temperatures the y fcc structure transforms to an fcc form with a much smaller lattice parameter, termed a cerium. A bcc form, 6, which exists just below the melting point (800°C), will not be considered further in this work. There is a substantial body of experimental evidence (reviewed by Gschneidnerl) which favors the acceptance of these four allotropes, though some investigators have tried unsuccessfully to observe the ß hexagonal form.'-' There is disagreement, however, over the phase-transformation temperatures, due, in part, to broad hysteresis and overlapping of the transformations between the a, ß, and ? forms. The transformations are also sensitive to prior thermal and mechanical treatment. The differing purity of cerium used by different investigators is undoubtedly a factor. Cerium is difficult to separate from other elements and is quite reactive, igniting spontaneously when it is filed in air. The highest purity of cerium to date is reported to contain several hundred parts per million by weight of impurities, and early investigations were carried out on cerium containing several percent of impurities. There have been reports of more than one fcc allotrope at room temperature. Gschneidner, Elliott, and McDonald5 obtained diffraction patterns of an fcc phase with a lattice parameter about 1 pct less than that of the ? phase, instead of the y phase, on slowly cooling cerium filings from 23° to -198°C and warming them back to room temperature. However, when the sample was heated to 447°C and cooled to room temperature it consisted of only the ? phase. They have designated this new fcc phase "a-? intermediate", and say it is quite sensitive to impurities. After prolonged high-temperature treatment of a powder specimen, Weiner and Raynor2 obtained a diffraction pattern of an fcc phase of lattice parameter about 1 pct less than the ? phase. This they called the y' phase. It could not be reconverted to the y phase and is claimed to be different from the a-? intermediate phase.5,6 Dialer and Rothe3 reported two fcc phases* after cycling their powder specimens between room temperature and -192°C. Gschneidner, Elliott, and McDonald5 suggested that one of the fcc structures obtained by Dialer and Rothe was equivalent to their "a-? intermediate" phase. Table I presents some pertinent data on the proposed allotropes. For the ?(fcc)-ß(hexagonal) transformation

Jan 1, 1967

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By F. C. Oliphant, George H. Fancher

Two samples of drilling mud from the Hastings oil field, Texas, were tested, and the solids in each were separated into small fractions of a limited range in particle size. The mineral composition of each fraction by X-ray analysis is reported, and the results are interpreted in relation to other measured quantities, such as the physical properties of the original samples and the density of the various fractions. It was found that only 7 to 8 per cent by weight of the solids was of colloidal dimensions and that neither of the samples contained montmorillonite but did contain illite. Considerable calcite was also found. These data should be useful to the geologist interested in the origin and history of sedimentary strata as well as to the petroleum engineer. Introduction The questions, What is good drilling mud? What constitutes bad drilling mud? are pertinent, because the proper use and control of drilling fluids has been a factor of great importance in the successful drilling and completion of oil wells since the days of Captain Lucas. Adequate control of the characteristics of drilling fluids has assumed greater significance comparatively recently because of the problems introduced by caving formations in deep wells, costly blowouts and impressive mud bills. Much is known about the solution of some of the problems but, despite extensive research directed toward a better understanding of the physical and chemical properties of clay suspensions, it is difficult to define precisely a drilling mud, and much more difficult to say what constitutes a good mud. It is generally believed that the smaller particles of a drilling mud greatly affect its physical properties. In fact, it is customary to blame the colloids in a mud for nearly everything that goes amiss, because colloidal properties have effects out of all usual proportion on viscosity, filtration rate and reaction to electrolytes. It is germane to know whether drilling muds possess colloids and if so, the quantity and kind. Source oF Samples Two drilling muds from the Hastings oil field, Brazoria County, Texas, were selected because it is generally agreed that in this oil field good natural muds made solely from formations penetrated by the drill can be used until the well is nearly ready for completion. Customary drilling procedure in this field is to spud in with water, set a protective string of pipe, drill to 2500 ft. and set the surface casing. Drilling is continued to 5500 ft. with no treatment of the drilling fluid other than addition of water to

Jan 1, 1943

By F. C. Oliphant, George H. Fancher

Two samples of drilling mud from the Hastings oil field, Texas, were tested, and the solids in each were separated into small fractions of a limited range in particle size. The mineral composition of each fraction by X-ray analysis is reported, and the results are interpreted in relation to other measured quantities, such as the physical properties of the original samples and the density of the various fractions. It was found that only 7 to 8 per cent by weight of the solids was of colloidal dimensions and that neither of the samples contained montmorillonite but did contain illite. Considerable calcite was also found. These data should be useful to the geologist interested in the origin and history of sedimentary strata as well as to the petroleum engineer. Introduction The questions, What is good drilling mud? What constitutes bad drilling mud? are pertinent, because the proper use and control of drilling fluids has been a factor of great importance in the successful drilling and completion of oil wells since the days of Captain Lucas. Adequate control of the characteristics of drilling fluids has assumed greater significance comparatively recently because of the problems introduced by caving formations in deep wells, costly blowouts and impressive mud bills. Much is known about the solution of some of the problems but, despite extensive research directed toward a better understanding of the physical and chemical properties of clay suspensions, it is difficult to define precisely a drilling mud, and much more difficult to say what constitutes a good mud. It is generally believed that the smaller particles of a drilling mud greatly affect its physical properties. In fact, it is customary to blame the colloids in a mud for nearly everything that goes amiss, because colloidal properties have effects out of all usual proportion on viscosity, filtration rate and reaction to electrolytes. It is germane to know whether drilling muds possess colloids and if so, the quantity and kind. Source oF Samples Two drilling muds from the Hastings oil field, Brazoria County, Texas, were selected because it is generally agreed that in this oil field good natural muds made solely from formations penetrated by the drill can be used until the well is nearly ready for completion. Customary drilling procedure in this field is to spud in with water, set a protective string of pipe, drill to 2500 ft. and set the surface casing. Drilling is continued to 5500 ft. with no treatment of the drilling fluid other than addition of water to

Jan 1, 1943

By William B. Phillips

The possible sources of potash salts in the United States have been considered from many points of view during the last several years, but it is only within the last two or three months that the situation has become acute. We import from Germany, the only sourcc of large supply, more than $10,000,000 worth of potash salts annually, and this business has been badly crippled by the European war. If there was ever a time in our industrial existence when the necessity of providing for our own needs was more acute than it is now, we are not aware of it. One has only to study the price lists of chemicals sent out by the large supply houses to see the change wrought within a very short time. Whether or not these prices are to maintain for a considerable time, no one can say; but it appears to be probable that we shall not see prices materially lower for a period of uncomfortable length, to say the least. It is not my purpose at this time to discuss the various sources of supply of potash salts that have been suggested or recommended. Some of them might afford a pleasing relief but all of them combined would not affect the situation seriously. If we are to have our own sources of potash salts, they will have to compare, in some efficient manner, with the sources upon which we have drawn during the last 20 or 30 years; i.e., they must exist in minable quantities. It seems to me to be quite idle to speculate upon our domestic sources of potash if those sources are not of a character similar to those upon which we have so long depended. A few thousand or, perhaps, a few hundred thousand dollars' worth of chemically derived potash may be produced under the stress of present conditions, but when we consider that each year demands more than $10,000,000 worth, we must look to underground sources; we must look to mines similar to the famous Stassfurt and Halle deposits. If we cannot mine potash salts, we shall have to do without them for a while.

Jan 1, 1915

By James T. Waber, Allen C. Larson, Karl Gschneidner, Margaret Y. Prince

The original graphical method proposed by Darken and Gurry for predicting which elements are soluble in a given element was slightly modified and was used to predict terminal solubilities in 1455 known binary combinations. it was found that the modified Darken and Gurry method had a reliability of 61.7 pct in predicting extensive solid solubility (greater than 5 at. pct) and of 84.8pct in predicting limited solid solubility (less than 5 at. pct), an over-all reliability percentage of 76.6. Using the same experimental data, it was found that using only the simple Hume-Rothery size-effect criterion was 50.1 pct reliable in predicting extensive solid solubility, only slightly better than a purely random choice. and 90.3 pct reliable for predicting limited solid solubility, an over-all reliability percentage of 67.6. THE first rational rules for determining a priori whether two metals are not freely soluble in the solid state were announced by Hume-Rothery and coworkers.1,2 These well-known rules have been accorded a special place in metallurgical literature. Since the "electronegative" and "relative valence effect" rules of Hume-Rothery were only qualitative in nature it was difficult to use them in a quantitative analysis. The next major step was made by Darken and gurry3 and apparently went unexplored for a number of years. They prepared graphs illustrating the influence of both electronegativity and size difference on the solubility of elements in silver, magnesium, and aluminum, and they drew elliptical figures, whose maximum width was ±15 pct of the solvent radius and the maximum height was ±0.4 electronegativity units. The purpose of the present paper is to assess and compare the effectiveness of using the simple size-factor and the Darken-Gurry criteria to predict which elements will be soluble and insoluble in a given solute. In 1957, waber4 prepared Darken-Gurry plots for determining the solutes that were likely to be soluble in 6 and plutonium and introduced an inner ellipse as an aid to determining which elements should be soluble to a considerable extent. As illustrated in Fig. 1, the major axis of the outer ellipse corresponded to ±0.4 electronegativity units (OD) while the minor axis corresponded to ±15 pct of the radius of the solvent phase (OB). This simultaneous "action" of the two Hume-Rothery criteria was used to indicate which elements would have little or no solubility in the host lattice, namely those elements whose points lay outside this ellipse. An inner ellipse, "centered" over the same point of the solvent was drawn with ±0.2 electronegativity units (OC) and ±8 pct (OA) as the major and minor axes. Solutes with points lying within the inner ellipse were expected to be capable of forming extensive solid solutions with the host element. Use of this method of applying the earlier Hume-Rothery criteria was moderately successful for plutonium. For 6-phase plutonium, only one element out of the eight predicted to be extensively soluble was known to be almost insoluble, and of the sixteen elements predicted to have more restricted solubility, five were known to be essentially insoluble. The success of discerning solubility in the E phase by this method was comparable. One prediction made on the basis of this analysis was that the heavier rare earth metals, such as holmium, erbium, and thulium, should be soluble in the 6 phase, whereas the lighter rare earth elements, such as lanthanum or

Jan 1, 1963

By T. P. Floridis, J. H. Young

The need for close control of the phosphorus content of steels has led to numerous investigations on the equilibria of the dephosphorization reactions. Winkler and chipman1 have established the general conditions for effective dephosphorization of steel. They are high slag basicity, high oxygen potential, and low temperature. Other investigators have made additional contributions to the understanding of the dephosphorization process. The current status of the understanding of the dephosphorization of steel is concisely presented by Bodsworth2 and by Ward. The investigation reported in this communication was undertaken with the purpose of establishing the effect of additions of barium oxide and calcium fluoride on the dephosphorizing capacity of slags. Esin and Gel'd4 proposed that barium oxide, being more basic than calcium oxide, should cause an increase in dephosphorizing capacity when added to steelmaking slags, or when used as a substitute for calcium oxide. Derge5 has also proposed that in the future conventional slags might be replaced by BaO-Al2O3 slags. There is, however, no experimental evidence confirming the effect of barium oxide on the dephosphorizing capacity of slags. The effect of calcium fluoride on the dephosphorization of steel is not clearly understood. It is generally recognized that additions of calcium fluoride are beneficial. It is not clear, however, whether calcium fluoride affects the equilibrium of the dephosphorization reaction, or whether it simply causes an increase in the fluidity of the slag and, consequently, faster approach to equilibrium. The experimental procedure consisted in equilibrating synthetic molten slags with liquid copper at 1550°C under a gas stream containing argon, hydrogen, and water vapor. In all experiments the argon to hydrogen ratio was approximately 4:1, and the hydrogen to water ratio was 5.42:l. Molybdenum crucibles were used as containers for the slag and metal. Under the above-described conditions of temperature and composition of atmosphere, there was no observable attack of the crucibles by the metal, slag, or atmosphere. Copper was used instead of iron, because iron attacks molybdenum. The equilibration was made in a tubular furnace consisting of a recrystallized alumina tube. The alumina tube was heated by electrical resistance. A Pt-40 pct Rh wire winding was used for most runs. A silicon carbide tubular resistor was also used for some runs. Temperatures were measured with a Pt-Pt-Rh (10 pct Rh) thermocouple and kept constant within ±5°C. Equilibrium was approached from both sides, i.e., by adding the phosphorus either as oxide in the slag or as a phosphorus-rich alloy of phosphorus and copper. The holding time at the equilibrium temperature was 6 hr. At the end of each run the crucibles were rapidly cooled and removed from the furnace. The slag and metal were separated and analyzed. The experimental results are shown in Table I. The phosphorus content of the slag is expressed both as percent phosphorus pentoxide and as percent phosphorus. The basicity ratio is computed by dividing the number of moles of basic oxides-oxides of barium, calcium, magnesium, and sodium—by the number of moles of acidic oxides- oxides of aluminum, phosphorus, and silicon. Calcium fluoride is not included in the computation of the basicity ratio; i.e., calcium fluoride is assumed to be neither basic nor acidic. The distribution ratio of phosphorus—percentage of phosphorus in the slag divided by the percentage of phosphorus in the metal- is plotted in Fig. 1 against the basicity ratio. The results indicate that slags containing barium oxide have greater dephosphorizing capacity than slags containing calcium oxide. The high dephosphorizing capacity of slags containing sodium oxide and the low dephosphorizing capacity of magnesia-containing slags which already have been reported in the literature2 are confirmed by the results of this investigation. It appears that calcium fluoride has a beneficial effect on the distribution of phosphorus between slag and metal in acid slags only. Although the obtained distribution ratios between the phosphorus contents of slag and copper are not directly applicable to the dephosphorization of steel, they are sufficient for evaluating the effect of slag additions on the dephosphorizing capacity of slags in general. An increase in the ratio of distribution of phosphorus between slag and metal indicates lowering

Jan 1, 1968

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By R. M. Asimow, J. J. Svitak

Tile crilical resoll,r,d shear stress, CRSS, for slip of slow1y cooled Ag-All single crystals was measured at 201K. Tlze importance of short-range order and Suzuki sogregalion was inrestigated by deter~rlining llze ciic.cl of quenching on the CRSS. Thr obserz.ed rfrtenching effects were generally small and indicate that short-range ordcr and Slczuki srgregation do no1 account for n significant portion of the solid-solution strengthening in this system. However, all alloys slzozcwi yield drops ulhich rilere heat- lreat nrenl-sensiline THERE have been a number of mechanisms proposed to explain alloy strengthening in the Ag-Au system. The effectiveness of some of the proposed mechanisms, especially those that depend on Suzuki segregation1" or on short-range order,2-6 SRO? should be strongly dependent on heat treatment. Since internal friction investigations in this system indicate that there is stress-induced order,' we must also consider the possibility of local atomic rearrangement or short-range ordering in the stress field of a dislocation. There is not complete agreement whether these mechanisms should be most effective in raising the flow stress, in causing yield drops. or some combination of these two effects. This work was undertaken to determine the effects in the Ag-Au system of mechanisms that depend on segregation or order by using known but drastically different cooling rates following a high-temperature treatment. By comparing the critical resolved shear stress, CRSS, for slip measured after a very slow cool and again after a fast cool (quench) of the same crystal, it is possible to determine the effect of cooling rate on CRSS* and on yield drops. The single-crystal CRSS was determined at several compositions because there has been no data published across the phase field since the publication of room-temperature flow stress by Sachs and Weerts.' EXPERIMENTAL PROCEDURE Starting with materials of 99.999 pct purity, single-crystal specimens of random orientation 1.25 mm square by 4 cm long were prepared with 0, 10, 14, 25, 30. 50, 70. 75. 80, 90. and 100 at. pct Au. Crystals were grown in an inert atmosphere using a modified Bridgman technique with a growth rate of 1.5 cm per hr in a gradient of 3°C per cm. To obtain a maximum practical degree of SRO, the crystals were cooled at a rate of 275'C per hr to about 310°C and then cooled at 6°C per hr to approximately 200°C. Specimens were tested in tension immersed in an alcohol bath at -72°C (201°K) at a strain rate > = 0.003 mm"1 to determine the CRSS (7). The activation volume of several crystals was determined from the flow stress increment (72 - T1) for a tenfold increase in strain rate. The total shear strain varied from 0.05 to 2.3 pct but was generally less than 0.4 pct. After testing, each crystal was then held at 500°C for 10 min, quenched into brine at -35°C and. after storage at -71°C for 1 day, retested in tension using a procedure identical to that of the first test. The quenching apparatus, see Fig. 1, was designed to enable accurate temperature control and rapid quenching while preventing specimen contamination and accidental deformation. Test data from a specimen with a fine thermocouple spot-welded to it indicated a cooling rate of 104C per sec. The relatively low heat-treatment temperature was chosen to minimize quenching defects caused by a large vacancy

Jan 1, 1970