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By Fred P. Dewey

Early last March Mr. Jerome Coldren, an old miner add prospector, undertook a prospecting tour through the western part of Kansas, and discovered a very peculiar bed of rock, which yielded a white metal on fusion with soda. Mr. W. D. Church, city chemist at Topeka, examined the metal and found it to contain nickel. This discovery created much excitement, and was at first doubted. Many samples of the material, from a range of twenty miles, were sent to the Smithsonian Institution for examination ; and in every instance a qualitative test showed the presence of nickel, although the amount appeared to vary greatly. The ore is quite different from any other nickel-ore. It consists of a quartzose conglomerate from bean-size down, with much decomposed material between the pebbles, and the whole cemented by a more or less manganiferous limonite. In the qualitative tests, the nickel appeared to vary with the manganese. In all the tests, simple treatment with HCI dissolved a great deal of AI2O3. The principal deposit is near the top of a small hill on the divide between Smoky Hill river and Butte creek. The surface-rock is the conglomerate, and, at varying distances, stains of the limonite appear and gradually increase ; so that the ore is simply the lower portion of a bed of conglomerate which has been heavily charged with the manganiferous limonite. Below the conglomerate is a layer of selenite; below this, a soft sandstone, containing well-preserved fossils, and below the sandstone, a shale. From 2 to 6 per cent. of nickel in selected samples has been reported by different chemists; but the following two analyses on large samples show the average composition of the material:

Jan 1, 1889

By F. W. Luerssen, J. F. Elliott

F LUSHING the early slag from a stationary open Fhearth having a high percentage of hot metal in its charge is necessary in order to remove silica from the system. The flush slag is strongly oxidizing and is somewhat acidic. It has, however, considerable capacity to extract phosphorus from the bath and it also removes considerable manganese. It seems probable that factors which control the distribution of phosphorus and manganese between slag and metal in the refining period also should be dominant in the flush and postflush periods. Several studies, as summarized elsewhere,1,2 support the viewpoint that conditions closely approaching equilibrium for these elements are rather readily established during the refining period. Over the years these studies have repeatedly demonstrated that 1—high slag v01ume, 2—low bath and slag temperature, 3—basic slag, and 4—strongly oxidizing slag favor rapid elimination of phosphorus from the bath to the slag. They also show that the following conditions favor retention of manganese in the bath: 1—low slag volume, 2—high bath and slag temperature, 3— basic slag, and 4—minimum oxidizing power of slag. When it is considered that the flush slag often carries as high as 75 pct of the manganese charged and only 25 to 60 pct of the phosphorus charged, it is evident that in removing silica much manganese is sacrificed but phosphorus removal is far from conplete. Because of overriding circumstances, this is accepted in most operations and actually it is considered to be inevitable. This may account for the fact that little attention has been paid to conditions affecting the elimination of phosphorus and manganese in the flush slag. A recent study of the behavior of various charge oxides has developed considerable information on the flush and postflush periods. Because the data are felt to be of general interest, they have been brought together and Presented in this paper. The object is to show the various factors in the flush and postflush periods which influence elimination of phosphorus and manganese. Physical Conditions During and After Flushing Physical conditions existing during the flush vary from plant to plant, from shop to shop, from furnace to furnace, and even from heat to heat. They are strongly influenced by the physical and chemical character of the charge oxide which is ordinarily necessary to provide sufficient oxidizing power early in the heat. Invariably the period is characterized by a vigorous reaction between the principal re-actants: the hot metal being added and the charge oxide. During the flush, it is probable that the slag acts to some extent as an oxidizer; but, because of the critical influence of the behavior of the charge oxid'e on flushing action, it seems apparent that the oxide itself is the dominant oxidizer. Fig. 1 shows the course of two heats which were selected as being typical of the group studied. Heat A was charged with 55 pet hot metal, based on the total metallics charged, and heat B had 57 pct hot metal. As indicated in Table I and Fig. 1, the melt-down slag, which is not usually voluminous and which is principally FeO, expands greatly in volume and will show rather high levels of SiO2, MnO, and P2O5 very soon after the beginning of the hot metal addition. Simultaneously, large volumes of CO are liberated which cause violent mixing of slag and metal. It is of interest to note that the time required to bring carbon down to a low level is very much longer than that required for the removal of silicon, manganese, or phosphorus. At the end of flush, carbon in the bath is still approximately 2 pct. When strongly reducing hot metal is brought into contact with strongly oxidizing conditions within the furnace! it is probable that the rate of mass transfer to the slag (and atmosphere) of silicon, manganese, phosphorus, and carbon initially depends principally on the rates at which the two participating phases are brought into contact That is, it depends on the nature of the various reactions. Later in the flush period, when the scrap is virtually all dissolved and the action of the bath has settled down to a steady and somewhat gentle boil, it is likely that other factors, such as the transfer of oxygen across the slag-metal interface, become dominant. The temperature of the slag-metal system is far from uniform. Heat is being driven by the flame down through the slag. Bubbling and surging of the metal also frequently brings portions of the bath in contact with the flame. At areas of contact between the ore and liquid metal, or slag and liquid metal, the oxidizing reactions generate much heat. On the other hand, scrap is being melted which tends to absorb large quantities of heat. Because the liquid bath is high in carbon, the steel scrap is brought into solution rapidly. This can proceed at a rather low temperature; and until much of the scrap has been taken into solution, the bath temperature would not be expected to increase appreciably. Consideration of these factors leads to the conclusion that during the flush period the slag should be rather hot and the bath relatively cold. Both observation and temperature measurements bear this out. Experimental Data The extended program of charge oxide evaluation permitted study of the widely varying conditions existing during the flushing period. Slag and metal analyses and bath temperatures reported herein (Tables I and 11) were obtained toward the latter portion of the work. Four different types of charge oxide, sinter, two types of hydraulic cement-bonded soft ores, and a pyrobonded agglomerate were used in the study. Although the heats reported were from only one 205 ton furnace, they show variations in flush slag analyses all the way from 25 pct FeO, which is typical with the use of a hard natural charge ore, to 45 pct FeO which resulted when a very poorly agglomerated fine ore was used. The physical behavior of the flushes showed a correspondingly wide variation from well controlled reactions to violent surges following periods of inac-

Jan 1, 1956

THE Bergbüchlein and Probierbüchlein occupy a unique position in the literature of mining and metallurgy, for, they are the first printed books on any aspect of the two related professions. The first printed book on any subject has an allure that may not be entirely warranted by the strict historical significance of its contents. Among the books of the first century of printing there are very few that contain information that was new at the time of publication. Much' of what they recorded had been previously circulated in manuscript form. Printed books are nevertheless of great value because they mark the time when the author's words, free from errors-or at least with the same errors-became available to large numbers, of readers, who thus could easily and cheaply acquire a common background for their future work. Moreover, though there is occasionally some doubt as to the exact year of publication'(as in the case of the present works), it is generally easier to date a printed work than a manuscript, and thus to provide a fixed coördinate in history. The Bergbüchlein, "The Little Book on Ores," is the first printed work in the field of mining. It is an introduction to mining geology, which means that it was not addressed to the practicing expert but was intended to rouse the interest of beginners in the various aspects of a future vocation. It touches on the theories of the generation of ores, introduces and defines some of the most frequently encountered technical terms of the profession, and indicates what knowledge and tools are required for successful prospecting and mining. It also describes the ores of the seven most important metals. For those parts that deal with theory the author accepted uncritically the traditional teachings of the alchemists and the astrologers; his hints on where to find promising ores are based partly on superstition; but, there is enough factual,

Jan 1, 1949

By Joseph E. Pogue

Any mechanism, either natural or artificial, for regulating the functioning of a given unit in the general economy must operate toward the maintenance of equilibrium if it is to survive. The petroleum industry, concerned as it is with the production of a natural resource of specialized character, is surrounded not only by the economic factors common to other industries but by an extra set of unique elements centering about the fugitive character of crude petroleum under conditions of competitive development. The term equilibrium, therefore, so far as the oil business is concerned, involves a combination of economic and physical factors: the first set having to do with supply, demand, costs, profit margins, purchasing power, and the like; and the second, with underground pressures in oil pools, efficient rates of extraction, and all other aspects of engineering that may be summarized by the familiar term "conservation." The two categories, in fact, are not as clearly divided as the foregoing statement would imply, for in practice it will be found that the economic and physical aspects have a pervasive interaction and interrelationship. If the development of the petroleum industry in the United States is examined from its inception in 1859 down to the present, it will be found that, beginning about 11 years ago, a new mechanism for regulating the production of crude petroleum made its appearance. Prior to this recent period, the production of this raw material was determined by competitive forces operating without outside restraints. At present the output of crude oil is subjected to supervision by regulatory bodies in most of the oil-producing states, which impose upon the operators certain conditions having to do with the manner and rates of production. Thus, in the space of a decade, the mechanism for producing crude oil has changed from an automatic to a designed procedure called proration. And in its short history this method has been marked by a rapid evolution in its nature and incidence, with progressive changes still under way.

Jan 1, 1938

By Joseph Pogue

ANY mechanism, either natural or artificial, for regulating the func-tioning of a given unit in the general economy must operate toward the maintenance of equilibrium if it is to survive. The petroleum industry, concerned as it is with the production of a natural resource of specialized character, is surrounded not only by the economic factors common to other industries but by an extra set of unique elements centering about the fugitive character of crude petroleum under conditions of competitive development. The term equilibrium, therefore, so far as the oil business concerned, involves a combination of economic and physical factors: the first set having to do with supply, demand, costs, profit margins, purchasing power, and the like; and the second, with underground pres-sures in oil pools, efficient rates of extraction, and all other aspects of engineering that may be summarized by the familiar term "conserva-tion." The two categories, in fact, are not as clearly divided as the foregoing statement would imply, for in practice it will be found that the economic and physical aspects have a pervasive interaction and interrelationship. If the development of the petroleum industry in the United States is examined from its inception in 1859 down to the present, it will be found that, beginning about 11 years ago, a new mechanism for regulating the production of crude petroleum made its appearance. Prior to this recent period, the production of this raw material was determined by competitive forces operating without outside restraints. At present the output of crude oil is subjected to supervision by regulatory bodies in most of the oil-producing states, which impose upon the operators certain conditions having to do with the manner and rates of production. Thus, in the space of a decade, the mechanism for producing crude oil has changed from an automatic to a designed procedure called proration. And in its short history this method has been marked by a rapid evolution in its nature and incidence, with progressive changes still under way.

Jan 1, 1938

By Jose M. Sobral

The approximate production of petroleum in the various fields and for the country as a whole is shown in the following table, the figures for the later months of the year being estimated. Among the developments of the year may be mentioned the finding by the Standard Oil Co. of a small production, about 6290 bbl., at Aguas Blancas in the Province of Salta near the Bolivian border, and of about 88,000 bbl. at Lomitas, near Tartagal in the same province. The Government (Yaciementos Petroliferos Fiscales) in the last four months of the year also obtained about 6290 bbl, from Quebrada Galarce. .The oil found in Salta is of good grade and while the quantity is small great hopes of larger production are entertained. Approximate Total Argentine Production for 1928 Barrels Barrels Comodoro Rivadavia............................... 8,165,615 Plaza Huincul..................................... 783,514 8,949,129 Distribution of Production Government, Comodoro Rivadavia................... 5,165,159 Government, Plaza Huincul......................... 306,166 5,471,325 Private, Comodoro Rivadavia....................... 3,000,456" Private, Plaza Huincul............................. 477,348b 3,477,804 a The companies represented are Astra, 649,474 bbl.; Oriente, 42,237; Ferrocar-rilera, 1,337,380; Comp. Indust. y Comm., 609,092, Solano, 64,158; Diadema, 298,114. b Standard Oil Co. and a few smaller companies, Exploratory drilling has also been conducted around the Comodoro Rivadavia field. The Government is drilling at Vuela del Senguer south of Colonia Sarmiento and about 200 km. west of the main field hut the prospect of success is not as yet large. The country around Castillo, where the Royal Dutch Co. has property, is regarded more favorably. perhaps the most interesting event of the year was the discovery of a productive horizon at Comodoro Rivadavia about 200 m. below that previously exploited. This new horizon was found by the Ferrocarrilera Co. at 769 m. in its well No. 81, the previous yield for this

Jan 1, 1929

By O. W. Rees, Gilbert H. Cady

Unit coal calorific values represent a close approach to pure coal values; they possess characteristics theoretically inherent in the latter values. They are essentially uniform in the same seam for areas possessing essentially uniform geological environment. They are higher in older than in younger coals in most cases, and in deeper than in shallower coals. In general, they display characteristics closely in accordance with expectation assuming that they are essentially indices of rank. Because it possesses these characteristics, the unit coal value is essentially a standard value, characteristic of each bed in each local region. Hence it can be used as a basis for determining the accuracy of results in newly established laboratories, or when new equipment is installed, or in checking the results of different laboratories, or even in determining the character of coal as mined or prepared if ash, moisture and sulfur values are known. DISCUSSION (A. C. Callen presiding) R. P. Hunson,§ Wayland, Ky. (written discussion).—One of the interesting observatioris made by the authors is that there is a more or less definite correlation between unit coal calorific values and the geological environment of the coal bed. It is very interesting to note that, in general, the unit B.t.u. value increases with the increase in the probable original depth of burial, and that each seam tends to increase in calorific value toward the areas of diastrophic instability. It is generally conceded that Parr's formula, for determining unit coal values, is about as accurate as any formula subsequently proposed for the same purpose. In his formula, Professor Parr did not differentiate between the sulfur present as iron pyrites and that present as organic sulfur. However, the practical application of the formula has shown that this is of little consequence. I agree with the authors that unit coal calorific values are useful ill determining the accuracy of calorimetric determinations, and in determining the character of the

Jan 1, 1934

By Dewitt T. Ring

Oil development in 1934 has been largely restricted to drilling offset and lease requirement wells. Practically no effort has been made to discover new fields, chiefly because of price structure and proration allowance. A summary of developments during 1934 of necessity is brief. No state agency is maintained for the collection of data. The State Bureau of Mines issues permits for drilling and inspects the plugging of wells in coal-bearing measures only. Therefore data are not in existence with which to compile tables similar to those in other papers of this symposium. Forty-seven counties in the state produce oil, productive depths ranging from 100 to 5300 ft. Approximately 35 different formations in Ohio have produced either oil or gas. These reservoir rocks occur through a stratigraphic interval ranging in age from the shallow Goose Run sand of the Upper Pennsylvanian in Washington County to the St. Peter sand of Lower Ordovician in Seneca County. However, 75 per cent of these formations are unimportant from the standpoint of real production. Most of the oil and gas in Ohio has been produced from the Clinton, Oriskany, Berea and Big Injun sands and the Trenton Lime. Of these, the Clinton is first and Berea second in importance. Fields The oil and gas-producing territory of the state can be grouped into five fields or districts, made up of a series of "pools" usually separated by nonproductive areas, and is in no sense a belt of continuous production. Trenton Field of northwestern Ohio, is scattered through 15 counties. Development began in 1885. This field reached its peak in 1896 with a production of 20,575,138 bbl. for the year. For 1934, production had declined to 990,000 bbl. The oil is classified as Lima grade. Clinton Field extends from the Ohio River in Lawrence County to Lake Erie in Lorain, Cuyahoga and Ashtabula counties. First Clinton-

Jan 1, 1935

By S. H. Ash

Mass production methods, although increasingly important for economic reasons, create new hazards, remove many hazards, and improve health and safety by reducing exposure and obtaining better supervision. Such methods must be efficient or be discarded. Skilled workmen are required who must be trained to utilize equipment that replaces picks, shovels, and explosives. The effects of working conditions on the health of workmen have long been evaluated in noncoal mines. Studies and action programs relating to environmental health hazards in the mineral industry have placed particular emphasis on dusts. The anthracite industry is conducting an action program on the problem of dust. Segments of the bituminous industry are now conducting similar investigations. An industrial hygiene survey of coal mining in the State of Washington has been conducted and the results published in 1949. (State of Washington, Department of Health, I. H. Bul letin 4.) Chest X rays were obtained from miners in the six major coal-producing counties. State Health Department mobile X-ray equipment was set up at most large mines. Participation was on a voluntary basis, and response was obtained from 70 percent. Important in successful mining safety programs are training programs for supervisors and workmen alike. These programs recognize that the employe is the focal point in injury prevention and are planned and function around him. During the war, industries had to compete with each other for workers and to obtain and hold good workers, working conditions had to be made attractive. The average age of the mine worker increased, and, contrary to what many expected, mining injury rates decreased rather than increased. To attract competent workers, risks to life and limb, as well as laborious tasks, have to be reduced, and an experienced worker is indispensable for safety. Young men are returning to modernized mines. Mass production methods and equipment are more to their liking; jobs are more remunerative, demand action, and require special training and skill that give them the mark of a craftsman. Such workmen can be taught safe methods.

Jan 1, 1950

By J. B. Rather

THE use of sulfuric acid in refining illuminating oils antedates the beginning of the petroleum industry in America by many years. It was used as early as 1792 by Tower in refining "coal oil" in the British Isles, and by 1860 there were 53 refineries in the United States manufacturing "coal oil," most of them using sulfuric acid as a refining agent. Following the completion of the Drake well in 1859, many of the "coal oil" refiners began to use petroleum for manufacturing illuminating oil, and their methods and equipment were adapted so far as possible to this new raw material. The value of sulfuric acid in refining "coal oil" having been established, this reagent was immediately tried and found to be satisfactory in refining petroleum. Notwithstanding the tremendous advances in petroleum technology since that time, sulfuric acid remains today the most valuable and most widely used means for refining petroleum products. EARLY METHODS OF DISPOSAL OF ACID SLUDGE With the almost immediate expansion of the petroleum industry came the problem of disposing of the acid sludge produced in the refining operations. While in 1859, the year of the discovery of the Drake well, a patent was granted for sludge separation and separated acid concentration, most of the earlier refiners, and many of their successors, felt that separation and recovery of spent acid was uneconomical. Accordingly, many of them disposed of the sludge in any way that seemed expedient at the time. It was buried in the refinery grounds, barged and dumped at sea, run into neighboring streams, or dumped into sewers. Some optimists carted it to open pits in the hope that it would either sink into the ground or evaporate. Not so many years ago, the superintendent of an eastern refinery, who was using the open-pit method of disposal, lost a sludge cart, with horse attached, in such a pit. The horse was recovered almost immediately, but its availability for further use was reduced to zero by the loss of its hair.

Jan 1, 1928

By E. T. Turkdogan, P. Grieveson

Experimental results are presented for the rate of solution of nitrogen in a iron in the temperature range 750° to 873°C and in 6 iron in the temperature range 1410° to 1470°C. It is shown that the rate controlling process is diffusion of nitrogen into the iron. The diffusiting of nitrogen in a and 6 iron is derived from the results, and the temperature dependence of the diffusivity is represented by the equation D = 7.8 x e- 18,900/RT sq cm per sec. The solubility of nitrogen in a and 6 iron, in equilibrium with 1 atm pressure of nitrogen, has been measured. Using these results and other available data, it is found that the variation of the logarithm of nitrogen solubility with the reciprocal of absolute temperature is nonlinear. In an Appendix, some results of Darken and Smith are presented for the rate of solution of nitrogen in iron using ammonia + hyidrogen mixtures. These data also support the view that diffudsion of nitrogen in iron is the rate-controlling process when ammonia + hydrogen mixtures are used. A considerable effort has been made to obtain data on the solubility1-5 and diffusivity of nitrogen in a iron6-l2 because an understanding of the effect of nitrogen on the properties of steel must be based on an accurate knowledge of the properties of nitrogen in pure iron. However, no information is available concerning the kinetics of solution of nitrogen in a and 6 iron. Recently the authors13 have investigated the rate-controlling mechanism operating in the kinetics of solution of nitrogen in y iron. This study was directed to determine the rate-controlling processes for similar reactions with a and 6 iron as well as to establish values for the solubility of nitrogen in equilibrium with nitrogen gas in a and a iron. EXPERIMENTAL The procedure used in experiments to determine the rate of solution in cylindrical iron rods was the same as that described in a previous communication.13 Ferrovac E grade iron used in all experiments contained the following impurities in weight percent: C, 0.005; Mn, 0.001; P, 0.002; S, 0.006; Si, 0.006; Ni, 0.025; Cr, 0.002; V, 0.004; W, 0.02; Mo, 0.01; Cu, 0.001; Co, 0.01; 0, 0.007. After cleaning the surface, the iron rods were treated in an atmosphere of purified hydrogen for 17 hr before the reacting gas was introduced for known experimental times. After quenching, the samples were sectioned radially and analyzed for nitrogen. In addition to experiments using rods, iron foils were used in the measurements of solution rates of nitrogen in a iron. The foils of two different thicknesses were prepared by cold rolling Ferrovac E grade iron cylindrical rod to 0.051 and 0.152 cm. Foil samples were used in a rectangular form 5 cm long and 1.25 cm wide. The specimens were thoroughly cleaned of surface oxide with fine emery cloth and degreased with carbon tetrachloride immediately before entry into the furnace. The experimental procedure was the same as that used in the study with rods. At the completion of an experiment, the foil samples of the nitrogenized iron were analyzed for nitrogen after discarding 0.3 cm from the perimeter of the specimen. Iron foils were nitrogenized and denitrogenized in the a and 6 range with a gas mixture of 95 pct N and 5 pct H for times varying from 5 min to 2 hr. Results obtained for the average composition of nitrogen in iron for these experiments are presented in Fig. 1. Prior to the denitrogenization experiments, the samples were saturated with nitrogen at 1000°C and 0.67 atm N, giving a uniform nitrogen concentration of 0.0204 pct. According to the known a-y phase boundary in the Fe-N system,14 this composition lies within the ferrite region at temperatures 750" to 850°C. Use of this initial nitrogen content insured that reaction occurred between the gas and a single solid phase, a iron. Examples of the results for the mean concentrations of nitrogen in cylindrical iron rods, 0.356 cm radius for both the a and 6 ranges are given in Fig. 2. Typical examples of the results obtained for the radial distributions of nitrogen in rods are presented in Fig. 3. It appears that the results for radial distributions can be extrapolated to constant surface compositions which agree with the equi-

Jan 1, 1964

By William Y. Holland, Roger M. Cook

In view of the increasingly widespread deterioration of concrete structures as the result of the interaction of the alkalies sodium and potassium released by hydration of portland cement and susceptible rocks and minerals in aggregates, it is believed that a paper summarizing the geographic distribution of these aggregates will be of interest to producers and users of concrete, concrete products, and concrete-making materials. THIS paper reviews the problem of alkali-aggre-gate reaction in concrete and describes the geologic and geographic occurrence and distribution of alkali-reactive sand and gravel in western United States. It includes no discussion of crushed stone or synthetic aggregates. Most deposits of sand and gravel are accumulations of particles of rocks and minerals from a variety of sources, and it is not unusual for at least one or two varieties of the rocks to contain some form of reactive material. Examination by petro-graphic methods of many sands and gravels, as well as manufactured aggregates, has shown that a comparatively high proportion of the deposits does contain, in greater or lesser degree, rocks and minerals known to be deleteriously reactive with the alkalies of cement. Fortunately the amount of reactive materials is commonly less than that necessary to cause deleterious effects in concrete. As investigation of unsound concrete structures progresses, it becomes evident that the alkali-aggre-gate reaction is even more widespread than supposed, Figs. 1 and 2. Even though some parts of the country appear at present to be immune, further investigations will probably show that the effects of alkali-aggregate reaction can be seen in many structures in these areas, although only on a small scale in most of them. Many concrete structures will, of course, have lived their useful life before disintegration from this cause is serious, and in others the alkali-aggregate reaction may never become significant even though the microscopic evidence of reaction is present. The alkali-aggregate reaction first was reported to be a cause of deterioration of concrete in 1940 when Stanton1 described expansion of concrete pavements in California. Similar expansion and deterioration of concrete was recognized during succeeding years in concrete structures located in many parts of the country, but particularly in the western states. A number of concrete laboratories2 became interested in the problem. It was soon determined that only certain combinations of aggregate and cement caused the alkali-aggregate reaction to take place, and moreover that the reaction progresses only in the presence of water. Further research proved that cements containing more than 0.60 pct total alkalies (pct Na,O + 0.658 x pct K2O), when used with aggregates containing appreciable amounts of reactive ingredients, caused the reaction to take place, usually with subsequent deterioration of the concrete. During the last few years this limitation has been adhered to in both government and private construction as the maximum allowable alkali content of cement to be used with aggregates of known alkali reactivity. Because of this limitation, it appears that deleterious reaction either has been reduced or eliminated in many recently built structures in which it probably would otherwise have occurred. Recent tests have shown that the degree of expansion obtained with any particular cement-aggre-gate combination depends not only on the alkali content of the cement but also upon the relation of this alkali content to the amount and degree of reactivity of reactive constituents in the aggregate.' In laboratory mortar bars, opal and cements with alkali content of as low as 0.2 pct (as equivalent of Na2O) have produced deleterious expansion as the result of alkali-aggregate reaction. These experiments demonstrate that aggregates containing even 0.1 pct of opal are deleteriously reactive. It was soon determined that alkali-silica gels were formed by the interaction of the alkalies of the cement and the reactive aggregate, Figs. 3 and 4. Osmotic or swelling pressures produced by the continued hydration of these gels cause expansion of the concrete with resulting cracking, warping, and dislocation. Evidence of the alkali-aggregate reaction can be seen by a petrographic study of the deteriorated concrete. Among the first structures studied by this method was Parker Dam on the Colorado River, California-Arizona. In the concrete from this dam pebbles of rhyolite, andesite, siliceous limestone, and chalcedonic chert were found to be reactive.

Jan 1, 1954

By C. G. Dunn, F. Lionetti

W. G. BURGERS*—It seems almost certain that this investigation shows the way which finally, when more analogous data have been obtained, must lead to the understanding of many features of preferential growth-directions of crystals and of the occurrence of recrystallization textures. In this connection I should like to mention that Mr. Tiedema in my laboratory succeeded in developing an analogous method for preparing crystals in aluminum plates with a chosen crystal-lographic plane and direction parallel to the surface of the plate (to be published in Cryst. Ada). If such crystals were grown in high purity aluminum and test-pieces containing a few crystals such as the authors describe were prepared for this metal, it might be possible that due to the absence of growth obstructing particles, even in this low-melting point metal boundary displacements approaching equilibrium positions might be realized. With regard to the apparently marked drop in surface energy for orientation differences approaching zero degree, and orientation differences approaching those existing between twins, it seems of interest to remark that in aluminum a crystal growing at the expense of fine grained material cannot (or can only very reluctantly) absorb grains in either ap- proximately (within 5—10°) parallel or spinel twin orientation (May, Tiedema and Burgers, Nature (1948) 162, 740 and Cryst. Ada in press). Consequently with aluminum the method of preparing a crystal with a definite orientation does not succeed when the new crystal has to absorb its own texture; for example it is not possible to grow in a polycrystalline wire with a [lll]-texture a crystal with a [11 Indirection parallel to the wire axis (Tiedema: Cryst. Ada, in press). Finally I should like to mention the well-known fact (Burgers: Proc. Acad. Amsterdam (1947) 50, 723) that prolonged annealing of recrystallized nickel-iron sheet with cube-texture never succeeds in transforming this into one single crystal of the same orientation; if, by "secondary re-crystallization," large crystals are formed

Jan 1, 1950

R. M. Raymond, New York, N. Y.—The filling and drawing down of the overhead material was done at considerable depth, which is not the usual method in which it starts at the surface.. R. J. Mechin.— It is a little more than 1000 ft. at El Bordo. The vein above had been caved practically to the surface and some of the ore had been excavated, using underhand and overhand square-set methods. This was far enough away from the shaft to prevent any bad effects. When the sill floor was taken out, to insure the old cave material following down well, we put chutes in the square sets for several weeks until we were sure that the material from above was moving down; on each level above, several crosscuts were driven into the old fill by which we could see the material coming down and thus be sure it was following the first. We had to dynamite it very little because it was dry and dusty. The only trouble was that timber starting from the old square sets would get across the chute and hang up. R.. M. Raymond.—HOW many floors did you operate at once? R.. J. Mechin.—We would operate one floor through the whole length and prepare for the second. F. W. SperR, Houghton, Mich.—Could you have worked it in steps? R.. J. Mechin.—Yes; but working it all on one floor was much better for ventilation. The passage between steps would tend to become heavy and blocked and, as the passages from the mining floor down are usually filled with ore, there would be no way for the air to pass up. By means of doors and fans, air was driven to the extreme end of the orebody through the stope and up the other end; but it could have been worked in steps. F. W. SpeRR.—D the following-up material ever become so heavy that you could see weight on the caps before you had to take out the posts?

Jan 1, 1927

By James Quigley

As the outcrop mines in the West developed into underground operations, systems of ground sup- port were gradually evolved. In the early coal mines there was little need for support except near the dirt line in portals, where stone masonry was common. Where the top was shaley or broken, native pine props with light cross bars and legs furnished enough support even in Utah's 25-ft coal seams. As depth of workings increased, roofs and backs of the same general nature as those near the surface became more and more unstable and required more and more support. Some coal airways show this tendency very clearly. From the surface down the same type of roof shows deterioration which an experienced eye can translate into a measure of depth under surface rather than change in rock characteristics. Rock bolts, developed by various companies and by the U. S. Bureau of Mines, have become an effective substitute for timber in sections of some metal and nonmetal mines formerly requiring excessive timber support, and further use of war surplus landing mats, chain link fencing, and a new punched channel developed by one of the steel companies has enabled other mines to operate deposits where costs of timber and lack of clearance for timber support would have prohibited mining. The block caving mines have made extensive use of reinforced concrete underground to achieve similar ends under difficult conditions. Steel sets are standard in many Bureau of Reclamation projects, although these are usually covered in with concrete to make the permanent structures the Bureau's reclamation projects require. But the use of steel in mining operations is limited and has been confined principally to the iron ore mines of Michigan, Wisconsin, and Minnesota. Some mines have installed used rail as posts, caps, and crossbars, but a rail section is not suited for load carrying, and used rails are generally brittle, having a tendency to fail without warning when overloaded.

Jan 7, 1959

By Robert Ignouf

MY REMARKS, which I feel highly honored in being invited to make, shall be limited to a consideration of -the mining and metallurgical problems involved in this question; in fact, these problems alone might well be considered as suffi¬cient to explain the existence of the Ruhr situation and to justify the steps taken by France in this affair. Comparing the France of pre-war days with the France of the period following the Versailles treaty indicates clearly how the Ruhr question is a direct consequence of the new economic conditions which have prevailed in Europe since peace was signed between the Allies and Germany. Before the war, in 1913 for instance, the French out¬put of iron ore was 22,000,000 tons. This output, which decreased considerably during and immediately after the war, has about regained its previous level. It should be noted that 96 per cent. of the production of iron in France is obtained from the eastern part of the country, in the districts of Nancy, Briey,. Longwy, Metz, and Thionville. This concentration of practi¬cally all the iron mines into one district creates a very serious problem for France, involving strategic and economic consequences. The strategic problem arises from the fact that the whole iron resources of France lie close to the frontier of Germany, at a distance of only a few miles; hence it is of the' utmost importance for France to be assured that her eastern frontier shall not be at the mercy of a sudden invasion by an army which could in a few hours deprive France of her iron resources and render her powerless to defend herself. Invaded by her Eastern neighbor three times during the past 100 years, France has had dire experience with what such invasions mean for her. Wherever the German armies have passed, they have left an inefface¬able trail of desolation. France, therefore, intends to protect herself by sufficient and efficient guarantees against renewed invasions of her territory.

Jan 5, 1923

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,' it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert's apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By P. B. Mee

The secondary re crystallization behavior of two vacuum-melted, nominally 3 pct Si-Fe alloys has been studied, one alloy being produced from pure electrolytic iron and semiconductor-grade silicon and the other from commercial-purity hot band. The vacuum-melted and vacuum-remelted alloys were found to develop {110}(hhl) and {lll)(hkl), respectively, on annealing in high vacuum and {100}(0kl) and {11l}(hkl), respectively on annealing in pure hydrogen of dew point, < — 60°C. H2S doping of the hydrogen or annealing in commercial argon was found to effect a reversal for the vacuum-remelted alloy from (111) to (100) secondary recrys-tallization, while prolonged vacuum annealing at 2 x 10-6 Tow resulted in a tertiary re crystallization from (111} to (110). The growth selection of the {lll}(hkl) component was found to be governed predominantly by the {111}/planar misorientation, the maximum deviation of the resulting secondaries being 5 deg. It is considered that the driving force for {111}(hkl) secondary recrystallization arises from the preferential lowering of ?111, possibly by phosphorus or nitrogen diffusion, just as oxygen and sulfur under certain conditions have been found to preferentially lower ?100. When heavily cold-rolled metals are annealed at high temperatures, primary recrystallization usually occurs rapidly and may be followed by considerable grain growth. However, in the presence of a fine dispersion of inclusions1"3 or with a strong matrix preferred orientation4&apos;&apos; the matrix may be stabilized and a secondary recrystallization may then be effected. Also, in vacuum-melted Si-Fe it has been shown possible to develop {100}(001) and {110}(001)6 surface energy driven secondary recrystallization textures. Further, it has been found that, on annealing very pure metals, grain growth normally ceases when a grain size approximately twice the strip thickness is acquired, due to the formation of V-shaped thermal grooves which result in an equilibrium being set up between surface and grain boundary stresses. If, however, a surface energy difference ??s, exists between adjacent grains (of the order of a few percent of the grain boundary energy ?b), then according to Mullins8 a secondary recrystallization may be effected, since the grains having lowest ?s would grow at the expense of their higher-energy neighbors. For clean bee metal surfaces ?110 should be lowest; however, for 3 pct Fe-Si (100) secondary structures have frequently been developed and have been attributed by Walter and Dunn9 to an alteration of the relative surface energies due to the preferential chemisorption of oxygen on (100) planes. Kohler,10 however, indicated that this reversal may be achieved by employing minute quantities of highly polar compounds in the annealing atmosphere, i.e., sulfur compounds, in par- ticular H2S being beneficial in (100) growth. This work has been verified by Kramer" using {100)/{110} bicrystals, while Mager12 demonstrated the importance of sulfur diffusion within the strip. Detert13 has intimated that carbon may be responsible for the preferential lowering of ?110 although no direct evidence has appeared yet to support this supposition. It must , be appreciated that the above-mentioned examples of surface energy driven secondary recrystallization were obtained with very pure vacuum-melted materials with oxygen contents (which is now known to be a critical factor") less than 35 ppm. During the course of a textural study on Si-Fe it has been found that under certain conditions (111) secondary recrystallization can be obtained by what is believed to be a surface energy growth selection mechanism. The purpose of the present paper is to briefly describe this result and to try and postulate the possible causes. EXPERIMENTAL Two vacuum-induction-melted, nominally 3 pct Si-Fe alloys were produced, one from pure electrolytic iron and semiconductor-grade silicon designated A and the other from commercial-purity hot band, designated B.

Jan 1, 1969