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By N. H. Mannakee

SINCE the publication of the paper of Mr. Scholz, The Effect of Humidity on Mine-Explosions,' I have undertaken a study of the meager available data of barometric and temperature conditions it times of mine-explosions, and have arranged these data in a manner which may be of interest to other students of mine-explosions. This study covers the period from 1898 to 1909, during which an ever-increasing percentage of collieries has been ventilated by fans giving air-currents of high efficiency. Previous to 1898 this percentage was smaller than at any time since. The vari¬ous States have become, from time to time, more exacting in their demands upon poorly-ventilated mines. This general im¬provement in ventilation throughout the Appalachian field has undoubtedly brought about a condition which is annually the cause; .or a very important attendant, of the high percentage of fatalities in mine-explosions, through the daily passage of from hundreds to thousands of gallons of water, invisibly suspended in the air, carried out of the mines by the ventilating-currents during the existence of certain temperature- and humidity-conditions. There is a wide-spread opinion that these conditions exist from November 1 to March 31; but it is more likely that they have a much wider range, which varies from year to year. Certain years show an increase or decrease of rain-fall from the mean ; the daily temperature may fall far below or rise far above the mean established by a record of a period of years; and the daily humidity varies likewise. If mine-explosions are influenced by a lack of moisture in the mines, certainly it may be expected that the influence will be felt at times when the

Nov 1, 1909

By George W. Neumann

The mines and concentrator of Brunswick Mining and Smelting Corporation are located in the northern part of the province of New Brunswick, approximately 20 miles distant from the City of Bathurst. Discovery of the No. 6 orebody by diamond drilling in 1952 was followed by the finding in March 1953, of the larger and higher- grade No. 12 orebody, approximately six miles to the north of the No. 6 deposit. Original development was financed by St. Joseph Lead Co., and included a small open-pit operation with a 10C ton per day pilot mill at No. 6 orebody, shaft sinking and underground development at No. 1; orebody, and an extensive program of laboratory and pilot plant metallurgical research on No. 12 ore. These operations were suspended in May 1958, and remained in standby condition until June 1961, when the equity of St. Joseph Lead Co. was purchased by a group headed by M. J. Boylen, K. C. Irving, Maritime Mining Corporation, and the Patino Corporation. Construction of a mine plant and concentrator at the No. 12 mine commenced in October 1962 and the concentrator was placed in operation in March, 1961b. Preparation of the open pit mine for production, construction of the No. 6 Concentrator to produce bulk Pb-Zn-Cu-Ag concentrate from No. 6 ore, and construction of an Imperial Smelting Process smelter at Belledune were started in 1964 and placed in operation in September 1966.

Jan 1, 1970

By Charles T. Van Winkle

Until the advent of the porphyry coppers and the introduction of flotation which soon followed, crushing and grinding for many years proceeded along somewhat stereotyped lines, without important alteration in type of machinery. For the finer crushing and grinding, stamps, rolls, and various patterns of Huntington and Chilean mills were in general use. Ball-mills were in use abroad, but owing to their small capacity and the high cost of screens and steel, they never obtained much footing in the United States. Tube-mills were first introduced into the crushing departments of cyanide plants when it was found that for crushing finer than 30-mesh other types of crushing machinery were not efficient. In order to crush with one pass, these mills were made 18 to 22 ft. (5.5 to 6.7 m.) in length. Pebbles were used as a grinding medium and the mills were lined with either silex blocks or fragments of quartz or flint pebbles set in cement. While the cylindrical tube pebble-mill had been used to some extent in small installations of concentration mills, the first instance of its use on a large scale was at the concentrating plant of the Miami Copper Co., where 8-ft. by 22-in. (2.5-m. by 55.9-cm.) Hardinge mills were tried out against Chileans. The results of these experiments led to the gradual replacement of the Chilean by the Hardinge mill. Robert Franke published an article' describing the work done, comparing the two types of mills. At the same time, according to Franke, a test was run using a 6-ft. (1.8-m.) Hardinge ball-mill as a substitute for rolls for intermediate crushing on 1/2-in. material. According to Franke, this mill was soon discarded, since it was found that to obtain the desired product the mill must be limited in capacity. The Miami Copper Co. made no test with other types of ball- or pebble-mills. Following this example, others installed the conical type; and when the Inspiration Consolidated Copper Co. decided to build a concentrator, it adopted the conical mill. As the requirements for mills would be very large, it purchased manufacturing rights in the State of Arizona from the

Jan 1, 1918

By W. R. Crane

THE effect of mining in the red-ore mines of the Birmingham district has been observed for some time, but, except in a few localities, little difficulty has been experienced from disturbance of cover. Cave-ins near the outcrop and fracturing of the surface at greater distances are the most pronounced manifestations of disturbance, while limited areas at points distant from the outcrop and under greater depth of cover have actually subsided. There is no doubt but that in time, because of failure of pillars, extensive fracturing and widespread settlement of the surface will result, particularly along the slope of Red Mountain, where mining has been under way for many years. Were it not that the orebed is overlain by one or more water-bearing formations, the fracturing or settlement of the surface would not be serious; but because of these formations, fracturing of the top rock may in itself be of sufficient importance to warrant the adoption of protective measures. Until development openings and surface plants are transferred to Shades Valley, protection of the surface will probably not be considered imperative, as the area involved is not of particular value for agricultural or building purposes. Further, the collapse of pillars over a wide area may develop squeezes that, if not controlled, may jeopardize the integrity of the mines and necessitate a change in development, from slopes to vertical shafts, at a much earlier period than is now contemplated. The occurrence of heavy beds of strong tough materials at varying distances above the orebed make it doubtful whether any serious disturbance of the surface will be experienced at any considerable distance from the outcrop, although some settlement will probably take place. It is certain, however, that no great volume of water will enter the mines from fracturing of the Fort Payne chert bed, as this is known to be a compact and practically impervious formation beyond the leached zone. Not so much can be said, however, regarding other possible sources of water, as pervious beds and through faults that may be encountered in future mining operations.

Jan 8, 1925

By G. W. Elger, H. E. Bell, J. E. Tress, J. B. Wright

This paper describes laboratory techniques and subsequent results of US Bureau of Mines (USBM) research to produce chlorination-grade feed- stock from an abundant, low-grade, domestic, rock ilmenite ore. The research is part of the Bureau effort to devise technology that may help decrease US dependence on imported raw materials. A rock ilmenite containing about 46 wt % TiO2 was smelted in an electric arc furnace with coke, wood-chips, and Na2CO3 to separate most of the iron as pig iron and to form a low-iron, titanium-enriched slug. The slug was ground, pelletized, oxidized, and then sulfated with mixtures of SO2 and air in a continuous 4.5- to 9.1-kg/h (10- to 20-lb per hour) apparatus at 1023° to 122J0 K (1380° to 1740° F). The sulfated slug, containing 60% to 65% TiOb, was reground and leached in water at ambient temperature to decrease the combined levels of the troublesome calcium, magnesium, and manganese impurities from 7.0 to 1.7 wt 70. The final product was upgraded to about 8.4 wt % TiO2. This material is potentially suitable for chlorination in a fluidized bed reactor. The most favorable results were achieved with leached slug sulfated at a feed rate of 4.5 kg/h (10 lb per hour) and at temperatures of 1073° to 1123° K (1470° to 1560' F).

Jan 1, 1986

By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By O. D. Sherby

In 1938, Kanter' revealed that the steady-state creep rate of low-carbon iron alloys could be correlated by an activation energy expression, where the activation energy for creep, Qc, was found equal to about 90.0 kcal per mole for most of the alloys investigated. He suggested that creep at high temperatures might be controlled by some sort of solid self-diffusion process since the value of Qc was about equal to the known value for self-diffusion, Qd. Correlations were not further attempted along these lines until many years later, when new evidence2-8 was presented suggesting that Qc = Qd for many metals. This equality now appears to be established for ten metals (Al, Pb, Ni, Mg, Cd, In, a Fe, y Fe, Cu, and Au). This experimental fact prompted several investigators to postulate various mechanisms of dislocation motion which would yield an activation energy for creep equal to that for self-diffusion.7-9 Possibly the most accepted theory is that based on dislocation climb7 where a dislocation is envisioned to surmount a barrier by an atom-vacancy exchange process, thereby "climbing" from one slip plane to another. Such a model would suggest that the steady-state creep rate, i, should be directly proportional to the rate of self-diffusion, D, for a given creep stress. In order to more clearly reveal the relationship between creep and diffusion, and to eventually determine the correct model, it would be desirable to obtain data showing correlations between i and D, rather than with a comparison of the temperature coefficients, Q. It has been known for some time that the self-diffusivity of iron atoms is greatly decreased when body-centered-cubic (a) iron transforms to face-centered-cubic (y) iron. This has been ascribed to the more close-packed structure of y iron. The diffusivity ratio at the transition temperature is Da/Dy =350. Correlations of creep data for a and y iron5 reveal that the creep rates under a given stress at the transition temperature differ by about the same ratio (ea/ey 2 200). It would be difficult to reconcile these results on any other basis than that the diffusivity of atoms probably controls creep of iron in some very direct way. No other published data on other allotropic metals appear currently available for further checking such a possible correlation between i and D. Thallium transforms from a hexagonal close-packed (a) structure to a body-centered-cubic (ß) structure at 230°C (503°K) and the self-diffusivities of the two structures have been determined by shirn.10 His results are plotted in Fig. 1 where it will be noted that Dß/Da = 25 at the transition temperature. It would appear desirable, therefore, to determine the creep rates of polycrystalline a and ß thallium at the transition temperature, as well as determine

Jan 1, 1959

By G. R. Speich

The precipitation of the Feab and Fe,Ti Laves phases (MgZn, type, C14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been studied in the temperature range 500" to 800°C using hardness measurements, light and electron microscopy, and X-ray and electron diffraction. The Fe-Nb alloys contained 0.96, 1.67, and 3.80 pct Nb and the Fe-Ti alloys 3.5, 5.8, and 8.8 pct Ti. In both systems only the equilibrium Laves phase is formed, with nucleation occurring at grain boundaries, at dislocations, and in the matrix. No cellular precipitation or transition phases were observed. The precipitation of the Laves phase in a fine dispersion leads to significant hardening in both systems. The hardness of the aged alloys is proportional to the reciprocal of the square root of the interparticle spacing. The maximum solid solubility of titanium in a! iron is 9.0 pct Ti at 1280°C. THE precipitation of the FezNb and FezTi Laves phases (MgZn2 type, C 14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been investigated as part of a continuing study of the mechanisms of precipitation from ferritic binary iron-base alloys. The iron-rich portions of the Fe-Nb and Fe-Ti phase diagrams are shown in Fig. l(a) and l(b). The Fe-Nb diagram is essentially that given by ansen' with the more recent work of Hume-Rothery and Gibson2 added. Goldschmidt3 indicates that the FezNb Laves phase has a solubility extending from 32 to 55 wt pct Nb. The Fe-Ti diagram is also essentially that reported by Hansen.l The recent results of Nishimura and kamei, Murakami, Kimura, and Nishimura,' indicate that the FezTi Laves phase has a solubility extending from 22.5 to 30.5 wt pct Ti. The L/6 + FezTi eutectic temperature of 1298°C indicated by Kornilov and oriskina' has been adopted. The addition of niobium or titanium to iron lowers the 6 — y transformation temperature and raises the y — a! transformation temperature. This results in a closed y field in the Fe-Ti system, but the lower solubility of niobium in a! (6) iron results in a eutec-toid, 6 — y + FezNb, at 1200°C, and a peritectoid, y + FezNb —-a, at 989°C in the Fe-Nb system. The maximum solubility of niobium is reported to be 4.5 wt pct in 6 iron,' 1.0 wt pct in y iron,7 and 1.8 wt pct in a iron.' Some results from the present work indicate that the maximum solubility in a! iron is actually less than 0.96 wt pct Nb. The maximum solubility of titanium in a! (6) iron is somewhat uncertain since the early work of To faute and Butting-haus indicated a value of 6.0 wt pct while later work of Kornilov and Boriskina6 yielded a value of 14.0 wt pct. The present work indicates that the maximum solubility is actually 9.0 wt pct. In both systems the phase in equilibrium with the iron-base solid solutions is a Laves phase (Mg znztype, C14), FezNb or FezTi. Both of these Laves phases have a wide range of Solubility. The precipitation-hardening behavior of Fe-Nb or Fe-Ti alloys has not been studied extensively. Genders and Harrison' reported that binary Fe-Nb alloys hardened upon aging. Peter and Fisher7 studied the mechanical properties of Fe-Nb and Fe-Ti alloys quenched from different phase fields.

Jan 1, 1962

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941

By W. E. Howlett, R. L. Slobod

Jan 1, 1965

By J. F. Nicholas

THE angles between the crystallographic planes in cubic metals were originally given by Bozorth and have been republished many times. Recently, Salkovitz2 tabulated the angles for the hexagonal metals (magnesium, zinc, and cadmium). he most commonly used metal which does not fail into either of these groups is tin, which has a tetragonal structure with an axial ratio of c/a = 0.54558 (99.99 pct purity, 25°C).² ccordingly, Table I has been prepared giving the possible values for the angle, 4, between planes of the types {HKL) and {hkl). The formula used was: Hh + Kk + LI — cos? = —--------------—-----------— A [(H2 + K2 + L2-a2c2(h2 + k2 + r;)] All angles are given correct to the nearest minute as this is sufficient for all practical purposes. Every angle depends in a different way on variations in the value of c/a, but even in the worst cases a variation of about 0.0003 in this ratio is needed to vary an angle by l', which corresponds to a temperature change of 20 °C or can be caused by impurities.

Jan 1, 1952

By D. J. Cox, J. P. Conway, A. E. Gooch

A two-year test conducted by the USBM's Spokane Mining Research Center (SMRC) has proven the feasibility of the yielding rockbolt, a concept which may prove very useful to the mining industry by providing ground support under a variety of conditions. The yielding rockbolt was originally developed in South Africa3 to overcome the limitations of conventional bolting in rock subjected to high-stress or rock burst conditions. The yielding effect is obtained by fitting the bolt prior to thread rolling with a smooth-bore die of internal diameter slightly larger than the shank diameter but smaller than the rolled thread diameter.

Jan 4, 1977

Discussion of the paper of R. H. RICHARDS and BOYD DUDLEY, JR., presented at the New York meeting, February, 1915, and printed in Bulletin No. 97, January, 191.5, pp. 67 to 72. R. H. RICHARDS, Boston, Mass.-I believe that the manner of working for efficiency in almost all lines is to study the conditions of highest efficiency, and then to measure what is being clone. We can then see how near we have approached the highest efficiency. Spigots in practice often use many times the water theoretically needed. There are places where that is necessary for safety reasons. There are, however, places where it is unnecessary, and in these places it seems to me that this work of Mr. Dudley's will be a great help to the mill man to arrive at the greatest economy of water and highest efficiency. ALBERT R. LEDOUX, New York, N. Y.-A good many years ago I received a telegram from that distinguished engineer, Hamilton Smith, which simply said in substance: "I have discovered that liquids will flow faster from a square orifice than from a round orifice of the same area, under the same head." I wondered why he sent me the telegram, but some time afterward he told me that he had been making experiments along that line in Montana; that he thought the discovery was interesting

Jan 5, 1915

By P. J. Potter

PRACTICALLY all tin-base babbitt metals used in engine bearings are made to customers' specifications, which are many and varied. The copper ranges from 3 to 8 per cent. and the antimony from 4 to 13 per cent.; generally, the babbitt with lower copper content will contain from 4 to 8 per cent. antimony and that with higher copper will have from 7 to 13 per cent. antimony. The allowable lead content varies from 0.20 to 2.00 per cent. If a solder is used as a bonding material instead of tin, the resulting material in the finished bearing will have a higher lead content, but it would not be enough to bring the lead above specificational limits. Impurities such as iron, arsenic and bismuth should be determined in the tin before using to insure a uniform and high-grade product. These points must be considered when segregating and grading the waste that comes from the finishing operations on lined bearings.

Jan 1, 1929

By Howard A. Meyerhoff

IN western Argentina, in the Province of Mendoza and the Territory of Neuquén, there is a series of solid bitumen deposits which are claimed to be the most extensive in the world. In a linear belt 500 km (311 miles) long, roughly paralleling the axis of the Andes but occupying a variety of positions with respect to the orogenic structures, more than 100 outcrops have been reported. Approximately 70 of these have been prospected, and some mining has been planned or attempted for about half this number. Limited tonnage, high sulphur content, inaccessibility, labor shortages, and disastrous fires have taken a heavy toll among these operations, and in 1947, only 4 deposits were being actively mined, but 8 more were being explored and developed with a view to placing them in production. Inasmuch as these deposits are currently yielding a substantial fraction of Argentina's limited domestic supply of solid fuels, a brief account of the deposits and of the small industry based upon them will provide a commentary on Argentina's fuel problem. CHARACTER OF SOLID BITUMENS The solid bitumens of Mendoza and Neuquén are petroleum derivatives, as is indicated by the following ultimate analysis: [CONSTITUENTS PER CENT Hydrogen6.8 Carbon82.4 Nit.rogenI.6 Oxygen2.7 Sulphur2.2 Ash4.3 100.0] In physical appearance they bear a close resemblance to coal and are commonly called carbón. Their specific gravity has an extreme range of 1.10 to 1.777 in 36 samples weighed, but the average is between 1.14 and 1.24. The material is black, lustrous to dull, with blocky to sub-conchoidal fracture. Though brittle, the purest material is softer than anthracite and exhibits slightly more cohesion. This bituminous material is generally known as asfaltita or asphaltite, but definitive chemical studies indicate that the term asphaltite or grahamite can be applied correctly only to the exceptionally pure material of the Auca Mahuida district in Neuquén. Some other name should be used for the chemically variable bitumens found in all other districts, and the designation "asphaltitic pyrobitumen" has been proposed by Carlos A. S. Piscione.1 At the present time these bitumens, are finding favor as solid fuel and as a gas-producing medium. They yield heat values of 8650 to 9750 cal,2 or 14,500 to 16,750 Btu per pound, and in consequence of their excellent heating qualities and the scarcity of imported coal, they are marketed as far away as Buenos Aires at a price of go to 95 pesos, or approximately $22 to 23, per metric ton. In burning, the material swells and decomposes into solid, fluid, and gaseous fractions which burn violently though nonexplosively. Its combustibility has been responsible for disasters and virtually complete destruction at Mina La Esperanza and Mina Santa Marta, and for minor mishaps elsewhere, as at Mina Escondida in August 1947.

Jan 1, 1947

By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1'2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900' C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1' and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By Ernest G. Enck

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

Jan 1, 1960

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.