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By Manning W. Cox

Van Stone mine area is situated at the head of Onion Creek on the northwest flank of Gillette Mountain, Stevens County, Washington. The di strict was found during World War I, but the mine did not come into production until 1952. Production to the end of 1965 was 2,242,960 tons of ore that yielded 10,700 tons of lead concentrates and 120,000 tons of zinc concentrates. The area is part of the Selkirk Mountains Zinc-Lead Belt, or Kootenay Arc, extending from near Revelstoke, British Columbia, to Colville, Washington. A thick but incomplete section of Paleozoic marine formations occurs in the Kootenay Arc and is overlain by marine and continental Mesozoic formations. Both are invaded by Late Mesozoic-Tertiary batholiths. The belt is characterized by open complex folding and extensive high-angle and local thrust faulting. Principal ore deposits occur in the highly deformed carbonate rocks of Cambrian age-the Maitlen (Laib) and Metaline formations. The Van Stone mine occurs along a steeply S-shaped fold lying between the Kaniksu Batholith on the west and the Rogers Mountain Fault, a northeast-trending fault on the west flank of the Gillette Mountain Anticline, to the southeast. The fold is cut by northeasttrending faults containing notoriously irregular lamprophyric, diabasic, and pebble dikes. The host rocks, lower Paleozoic dolomites, are decolorized, silicified, and silicated in the mine area. Jasperoid and tremolite are the common alteration minerals. Other gangue minerals are barite, pyrite, brucite, calcite, and, near the batholith, pyrrhotite. Ore minerals are galena, jamesonite, and sphalerite. Ore minerals occur in bunches and pods intergrown with tremolite and jasperoid. Zinc is roughly eight times more abundant than lead. The highest ore outcrops at 3870 feet elevation, and an undeterminable portion has been removed by glacial scour. The lowest drill hole penetration has reached 3220 feet elevation. Oxidation ranges up to several hundred feet in depth and may be most closely related to pre-glacial groundwater circulation. The area of the mine was completely over-ridden by Pleistocene continental glaciers, and the present erosion surface is nearly continuously blanketed by up to 150 feet of glacial outwash.

Jan 1, 1968

By Albert Smith

THE creep properties of metals have as-sumed increasing importance in recent years and many investigations have been made on various phases of the problem. In the past year the annual lectures of the Insti-tute of Metals Division1 and the Iron and Steel Division2 were concerned with this subject, and are excellent reviews. For many years the creep properties of lead and lead alloys have been investigated at the Central Research Laboratories of the American Smelting and Refining Co., and it is hoped that the present paper will contribute knowledge of some of the factors that influ-ence creep. Lead, being a metal that recrys-tallizes readily at room temperature, is an excellent material upon which to investi-gate creep phenomena because of the sim-plicity of the apparatus needed, and it might be expected that results would apply to some extent to elevated-temperature tests of other metals.

Jan 1, 1940

By Svend Rordam

THE development of a cement that will resist the destructive action of sea water and other corrosive waters is a problem that has occupied cement chemists for the past one hundred years. It has been found that of the various salts that commonly occur in corrosive waters, sodium sulphate, magnesium sulphate and magnesium chloride are most destruc-tive to cement. Many investigations have been carried out in the United States, in Canada, and in Europe to solve the problem of what constitutes a sulphate-resistant cement, and during the past 10 years some of the findings give definite information in this respect. COMPOSITION OF CEMENT Portland cement is composed of four major compounds: 1. Tricalcium silicate 3CaO.Si02 (C3S) 2. Dicalcium silicate 2CaO.Si02 (C2S) 3. Tricalcium aluminate 3CaO.Al203 (C3A) 4. Tetracalcium aluminoferrite 4CaO.Al203.Fe203 (C4AF) The two calcium silicates are the main contributors of strength. The tricalcium aluminate contributes some to the early strength of the cement but has the least resistance of the four compounds toward the attack of sulphate waters. The tetracalcium aluminoferrite does not contribute very much to the strength, but is far more resistant to sulphate waters than the tricalcium aluminate. When hardened cement is exposed to water containing sodium or magnesium sulphates, these salts will react with the hydrated tricalcium aluminate in the cement and form compounds that will cause a swelling, disruption and crumbling of the hardened cement.

Jan 1, 1939

By W. C. Maurer

Although millions of feet of rock are drilled annually, the basic drilling mechanisms involved are not well understood. The primary reason for this lack of knowledge is because the basic principles of rock failure are not well understood and rock failure is the primary mechanism in drilling. A better understanding of the drilling mechanisms would enable a more scientific approach to the design and use of drills and bits. The paper reviews several models which have been proposed to explain various aspects of the different drilling methods. These models are described and their limitations and areas of application are discussed. Drilling rate relationships are developed and related to the basic rock failure mechanisms. TYPES OF MECHANICAL DRILLS There are three basic methods of mechanically attacking rock: 1) percussive action, 2) rotary action, and 3) combined rotary-percussive action. A percussion drill applies a force perpendicular to the rock surface and the bit moves into the rock perpendicular to the surface, forming a crater beneath it (Fig. 1). A rotary drill applies a constant thrust to the bit while a torsional force moves the bit parallel to the rock surface, breaking the rock ahead of it. A rotary-percussive drill applies both a rotary force and a percussive force to the bit which moves into the rock at an angle to the surface. The commonly used drills can be classified as: rotary-drag, diamond; percussive-hammer, piston, churn; and combination-rotary-percussive, roller.

Jan 1, 1967

By Clemens Jones

An interesting paper by J. E. Merion and Edward Hart, in Volume I., No. 2, of the Journal of Analytical Chemistry, on the Decomposition of Blast-Furnace Cinder by Acid, describes a plan of sampling the cinder by means of a previously-heated iron bar thrust into the cinder car or into the cinder at the notch, and then allowed to cool, thus chilling the cinder which adheres to the bar, and rendering it decomposable by hydrochloric acid, of 1.12 sp. gr. A short series of results is given, from which the deduction follows that blast-furnace cinder " is decomposed perfectly when chilled." Where many silica determinations are to be made, this method, if reliable, would effect notable economy of time and reagents. The conversion of insoluble silicates by fusion with an alkaline carbonate, together with the subsequent solution, evaporation, drying, etc., is destined to remain the standard method. But all fusionmethods are time-consuming and expensive. Chilling appears to render the supplementary method available for all practical purposes, in the determination of silica in cinder. But, with a view of securing more evidence on the subject, and in view of the fact that uniform results were not obtained by employing this method, it was decided to test the method in the laboratory of the Thomas Iron Company where a large number of silica determinations are made. The experience met with may not be devoid of value, both theoretical and practical. Mr. Iles's paper, in the Chemical News, Volume L., 1881, doubtless suggested to several chemists, connected with iron metallurgical

Jan 1, 1888

By W. W. Gorr, R. Smith, E. H. Wyche

THE combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W? and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. DEVELOPMENT OF THE NEW STEEL For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield 18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators 'then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, o.58; Ni, 7.28; Cr, 17.6o; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1946

By H. Margolin, E. Ence

Two versions of the Ti-Mn binary diagram have been published recently.' , -0th diagrams show two compounds in the region between 40 and 70 wt pct Mn, but disagree as to the reaction in which these compounds are involved. The investigation of the manganese-rich portion of the Ti-Mn binary diagram was undertaken at New York University as part of an investigation of ternary systems with titanium and manganese in order to determine which of the proposed diagrams is correct. A number of alloys between 31 and 70 pct Mn were prepared in a manner similar to that described by Cadoff and Nielsen; except that low currents (110 amp in argon atmosphere) and long melting times (up to 20 min) were used to prepare the alloys. Compositions were determined from weight-loss data, assuming all loss as due to manganese. Heat treatments were carried out with relatively large pieces, since there was a tendency for manganese to be lost during heat treatment. When X-ray diffraction data was to be obtained, the central parts of heat-treated specimens were used to make filings or powders which were not heat treated. Specimens were heat treated from the as-cast state. Heat-treatment times were as follows: 1150°C, 1 day; ll00°C, 2 days; 1000°C, 5 days; and 900°C, 15 days. It should be noted that equilibrium was not attained at 900°, 1000°, and in one case, at 1150°C. Metallographic specimens were electrolytically polished and strain etched by a technique described elsewhere.' At least four, and possibly six, phases were found in the region investigated. On the basis of information available at this time, a completely self-consistent diagram cannot be constructed, and therefore data are presented only for those phases which have been identified by both X-ray and microstruc-ture. Of the compounds detected, the one highest in manganese is the Laves phase, TiMn,, which is hexagonal with a MgZn, type of structure.V he diffraction data for TiMn2 from a 70 pct Mn alloy annealed at 1150°C are shown in Table I. The c/a ratio and parameters of TiMn2 agree well with those of Wall-baum hnd Rostoker et al. The values obtained here are c/a = 1.641, a = 4.825A. Another compound is the y-phase which is estimated to contain about 60 pct Mn. The y-phase has a structure which is identical to that of TiMn, with c/a = 1.639, a = 4.906Å. The fact that y has a Laves-type lattice would suggest that TiMn, has a range of solubility which extends from the composition of TiMn2 (69.6 Mn) to that of y (60 pct Mn). However, this could not account for microstructures which, in the 60 to 70 pct Mn region, show several phases in both the as-cast state and after annealing at 1150°C. Fig. 1 shows a two-phase structure of a 60 pct Mn alloy annealed at 1150°C. The phases present are y (white) and e (dark). If y were TiMn, then, according to Rostoker et al.,' the second phase of Fig. 1 should be P-Ti. The diffraction data for the 60 pct Mn alloy of Fig. 1 are shown in Table I. The starred d-values are from the e-phase and these lines do not correspond to those of &Ti. Comparison of as-cast and 1150°C microstructures of the 60 pct Mn alloy indicates that e precipitated from y. Since y has a

Jan 1, 1955

By John W. Chandler

INTRODUCTION Where and how to spend the exploration dollar to net the greatest economic return, has always been a major problem for mining companies. Minerals are being consumed in ever increasing quantitie: throughout the world and the mining industry is being called on to meet this demand. In view of the present world-wide nationalistic trend, it is becoming more difficult to determine where exploration money can be spent most profitably. An exploration project should be evaluated continually--in the beginning, to define economic targets and later to determine, as early as possible, whether a project has a chance of developing into a venture that will make a profit acceptable to top management. At this point, a decision can be made whether or not to proceed with plans to bring in a new mine. Exploration, evaluation, and development, therefore, must be fully integrated in transforming an exploration project into a profitable mining venture. DEMAND FOR LEAD AND ZINC Lead and zinc are metals basic to our economy and the demand for them will continue to rise as the population in the world increases. If the population continues to grow at the present rate, it will about double by the year 2000. The accelerating demand for these metals is shown by statistics. Nearly half as much lead (48%) and more than half as much zinc (55%) have been mined between the two world wars as in all pre- ceding history. (1)

Jan 1, 1970

By G. V. Woody, J. D. Price

Many producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. Overcoming Defects in Coke from Colorado Coals Colorado coking coals are all of the high-volatile type and were all laid down during the Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Poca- hontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-vol-atile coal was developed through low-tem-perature carbonization—or, more correctly speaking, through the partial devolatiliza-tion—of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By J. D. Price, G. V. Woody

Many producers of by-product coke have spent considerable time and given considerable thought to the use of a substitute for low-volatile coal as an admixture with high-volatile coking coal for charging high-temperature by-product coke ovens. Generally speaking, there are two principal reasons for this, one being occasioned by the lack, in certain localities, of low-volatile coal delivered at a cost sufficiently low to permit its use, and another being the desirability of finding a substitute product with a delivered cost lower than the cost of the low-volatile coal. It was for the first of these reasons that the Colorado Fuel and Iron Corporation was particularly interested in this subject. This paper deals with the experimental work and the results obtained by that company in producing and using low-temperature char. Overcoming Defects in Coke from Colorado Coals Colorado coking coals are all of the high-volatile type and were all laid down during the Cretaceous period, which makes them something like 80 million or so years younger, geologically, than eastern coals. They behave, when coked alone, something like the Pittsburgh-seam coals. They make a very brittle, highly cross-fractured, fingery coke of fair shatter value but quite low in resistance to abrasion. Mixed with a low-volatile coking coal such as Poca- hontas or certain Oklahoma coals, they make a coke that is equal to virtually any of the eastern cokes. The inferior quality of Colorado coke has long been recognized, and a considerable amount of time, effort and money has been spent upon investigations of means for improving its physical properties. While it has been found that some improvement in quality of coke can be secured by the adjustment and control of such variables as pulverization, moisture content, oven temperature and bulk density of charge, and through the addition of certain inert materials such as pulverized coke breeze, pitch, high-volatile noncoking or semicoking coal, the benefits so gained have been comparatively small. There are no low or medium-volatile coking coals available within a reasonable freight-cost distance. Therefore a substitute for low-vol-atile coal was developed through low-tem-perature carbonization—or, more correctly speaking, through the partial devolatiliza-tion—of high-volatile coals. The blending of this lower volatile char with the high-volatile coking coal distinctly improves the quality of coke made from Colorado coal. There is nothing especially new about this idea. In 1908 a Japanese patent was taken out by Kotaro Shimomura, whose claim was: The method of making a nonfingery coke out of bituminous coals, without using natural coals of low-volatile matter; according to which a certain coal is heated at a temperature between about 300°C. and about 600°C. so as to leave about 15 to 25 per cent volatile matter in the coal; this coal is mixed with the

Jan 1, 1944

By D. Turnbull, R. E. Cech

THE supercooling behavior of pure liquid metal droplets has been described.' The solidification behavior of small droplets of Cu-Ni alloys as a function of composition is described herein. The Cu-Ni system is of interest for such an investigation because the components are miscible in all proportions in both the liquid and solid state and the phase diagram of the system, Fig. 1, is a type often encountered in metal systems. It was noted by Van Riemsdyk2 and others that the nature of the "blick" of gold droplets during assaying is not perceptibly affected by the content of the platinum group metals that are soluble in both liquid and solid gold. With the exception of these very qualitative observations there appear to have been no prior investigations of the supercooling of alloy droplets. A series of nine alloys varying in composition by 10 pct (nominal weight) steps was made using certified OFHC copper, 99.996 pct purity, obtained from the American Brass Co., and electrolytic nickel pellets, 99.92 pct purity, obtained from the International Nickel Co. The alloys were melted and cast in vacuo in a high frequency induction furnace. Segregation was minimized by chill casting into 1-in. diam steel molds. Each alloy rod was homogenized at a temperature 50°C lower than the solidus for 100 hr in dry hydrogen. Samples for solidification experiments and chemical analysis were machined from the same portion of each rod and at a depth of in. from the rod surface. A Car-boloy tool was used in taking turnings to minimize contamination of sample by the cutting tool. As a check, a number of samples for microscopic observation were chipped from the ingot with a fragment of pyrex glass. The resultant data in all cases agreed, within experimental error, with the data obtained from machined turnings. A number of small particles, 30 to 50 micron diam, of a Cu-Ni alloy were placed in a quartz vial 1/32 in. diam x % in. long. This was inserted into a platinum ribbon heater and mounted in a high temperature microscope stage. The general procedure followed in inserting samples into the stage and measuring the temperature of melting and solidification was the same as described in an earlier paper.' A chromel-alumel thermocouple was used to study alloys of 88.93 pct Cu, 80.62 pct Cu, and 72.27 pct Cu. A platinum-10 pct rhodium thermocouple was used for the remainder of the alloys. Procedure The assembled high temperature microscope stage was first evacuated and the sample given a 2 min in situ treatment at 900 °C in dry hydrogen to remove surface oxides which might otherwise catalyze crystal nucleation. After this treatment the atmosphere was changed to purified helium and melting and solidification were observed microscopically. It was not possible to determine the solidus with certainty. However, the liquidus temperature was measured very accurately since the surface of the particle changed in appearance from coarse and uneven to smooth, mirror-like within a few degrees. The visually determined liquidus temperature was checked by finding the highest temperature to which the particle could be heated such that it did not supercool upon lowering the temperature. This temperature which checked within experimental error with that found by observing surface change was assumed to be characteristic of the thermody-namic liquidus. In order to minimize the effect of selective evaporation of copper from the alloy, samples were changed frequently and the droplets were heated no more than 50 °C in excess of the liquidus temperature T,. When the latter conditions were fulfilled, T, values were reproducible. After melting, the temperature was decreased slowly until the particles solidified. The sudden release of heat of fusion on solidification caused the

Jan 1, 1952

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.' Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By Harold Cook

THE purpose of this paper is to state briefly the inspection requirements of the Bureau of Ordnance, the specifications governing the inspection, and the physical and chemical properties of the steel used in the construction of ordnance for our Navy. It would be of interest to evoke discussion on points in these specifications which do not tend to insure the production of the very best material for the purpose intended. In other words, what requirements of our specifications are useless and also in what manner are our specifications deficient? It might be well at the, start to answer the first criticism of this paper which will probably be made, and that is that the title does not agree with the subject matter. Considering metallographic work as covering only the macroscopic and microscopic examination of metals, this paper will have gone beyond the subject; but it is believed that a broader definition of metallography is that it is the study of the relation of the internal structure of metals and alloys to their composition and to their physical and- other properties. The internal structure of steel is dependent on its physical and its chemical properties. These physical properties are dependent on the chemical composition and the mechanical and thermal treatment of the steel. So it seems that this subtitle would not be entirely necessary and that the title "Metallography of Steel for Ordnance Purposes" would cover a study, not only of what we can learn of macroscopic and microscopic examination, but broadly of the whole subject of the specifications, the fulfillment of the requirements of which produce the structural conditions revealed by macroscopic and microscopic examination. .

Jan 2, 1916

By J. W. Rutter, K. T. Aust

Observations are presented of the formation of annealing twins during the growth of a recrystallized grain into a striated, melt-grown crystal of high-purity lead. The formation of an annealing twin resulted in replacement of the original migrating boundary by a large-angle grain boundary of the caincidence-site type or by a near-twin boundary. The results support the Fullman-Fisher theory of annealing twins and demonstrate the usefulness of the coincidence-site model. FULLMAN and Fisher1 have advanced the following theory to account for the formation of annealing twins during grain growth. Whenever a grain A grows into a matrix of grains S1 and S2, a twin A' of grain A may form, as shown in Fig. 1, if the following energetic condition is satisfied: where "E" and "a" refer to the specific interfacial free energy and the area, respectively, of the boundaries indicated by the subscripts. In effect, the twinned grain will persist when the energy of the boundary between the twin(A') and the matrix grain (S, or S,) is less than that of the boundary between the original growing grain (A) and the matrix grain by an amount which exceeds the energy of the coherent twin boundary between A and A'. Experimental observations on the changes in grain boundary free energy accompanying the formation of twins1 are in agreement with the theory outlined in Eq.[l]. Direct observations of the formation of annealing twins at moving grain corners1"3 and the depend-

Jan 1, 1961

By Richard Smith

After a brief history of the phosphate industry of Tennessee, the distribution and origin of the phosphate rocks are described. Then the mining and treatment, together with costs of production, and the uses of the rocks are given. THERE are three distinct varieties of phosphate rock, in Tennessee, known commercially as: (a) the "brown" rock, which is the residual product of the weathering and natural concentration of certain phosphatic Ordovician limestones; (b) the "blue" rock, which is an unaltered phosphatic stratum of Mississippian or Devonian age; and (c) the "white" rock, which is the result of chemical replacement and deposition. Before 1894, South Carolina and Florida had supplied most of the phosphate of the United States, South Carolina leading until that date and Florida from then until the present time. In December, 1893, the blue phosphate of Tennessee was discovered almost simultaneously on Swan Creek, in Lewis County, by two independent parties-by one as the result of a careful and systematic search for a workable deposit of the long known kidney phosphate, and by the other through mistaking it for a "bloom" of coal. Leases were taken and, with further prospecting disclosing other deposits in the region, the development progressed as rapidly as could be expected without railroad transportation. In January, 1896, Judge S. Q. Weatherly, who was interested in the development of the blue phosphate, while riding along the road south of Mt. Pleasant, noticed some slabs of a brown rock in place above the limestone. He took samples, and had them analyzed, thus discovering the high-grade brown phosphate of this district. This discovery was kept a secret until July, 1896, when mining was started at the village of Mt.

Jan 9, 1924

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has had a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1790. Practically all of this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the "white man" Indians are known to have made salt from such salt springs as those that existed at Avery Island, La., Charleston, W.Va., Saltville, Va., and Onondaga, N.Y. In 1862 the first rock salt was mined in the U.S. from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, Va., and then at Retsof, N.Y., in 1885. Of the more than 40 million tons produced annually in the United States, about 68% or 27 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc.

Jan 1, 1975

By R. K. Hopkins

For a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950" to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as —75" F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But, when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service. A great deal of credit is due to the members of the Boiler Code Committee and also to the members of the Joint A.P.I.-A.S.M.E. Committee, who have formulated codes that insure the safety of the

Jan 1, 1935

By R. K. Hopkins

For a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950" to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as —75" F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But, when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service. A great deal of credit is due to the members of the Boiler Code Committee and also to the members of the Joint A.P.I.-A.S.M.E. Committee, who have formulated codes that insure the safety of the

Jan 1, 1935

By Wieland D. R., Hurst R. E., A. R. Hendrickson

Analysis of acidizing techniques, in correlation with reservoir data and a backlog of past treatments, has resulted in the development of a valuable engineering guide for planning acidizing treatments. Such treatments fall into three categories: (I) acid injection into the pores of the matrix; (2) acid injection into natural formation fractures at less than parting pressure; and (3) combination acidizing-fracturing treatments in which acid solutions (without propping agents) are injected at treating pressures sufficient to open and extend fractures through which the acid flows. Because the spending tirnze of acid during a specific well treatment does not change appreciably, maximunl penetration is attained when the first increment of injected acid is completely spent. Additional acid injection cannot be expected to further extend the benefits of the treatment. Depth of penetration will depend upon the reaction rate of the acid under treatment conditions, the injection rate of the acid into the matrix or fractures and the area-volume relationship existing in the flow channels. Based on Darcy's flow formula, extremely low injection rates must be used in order to keep bottom-hole injection pressures below formation fracturing pressure. As a result, only limited penetration of unspent acid will occur. Treatment records indicate that, in most acidizing treatments, formation parting pressures are exceeded, greatly extending acid penetration. Under these conditions, stimulation benefits are limited to the fracture area produced during the spending time of the first increment of acid injected into the formation. This area may be calculated from laboratory and well data to estimate depth of penetration. This, in turn, may be correlated with productivity data to assist The art of gas and oil well acidizing has been characterized by many changes in treating materials and techniques since its inception. These developments have been designed to provide greater production increases. prolong production declines and shorten payout time. Such improvements have been based primarily on data derived from laboratory research and field experience. As more of the variables influencing these treatments have been recognized and evaluated, acidizing has become less of an art and more of a science. Recent studies of fracturing treatments,' in light of individual well conditions and the results of thousands of fracturing treatments, made possible the formulation of an engineering guide that is now being used to select optimum treating techniques and to forecast probable results of such treatments. A similar analysis of the factors controlling acidizing treatments has been made and is the basis for this paper, The findings herein can be used as a guide in the selection of acidizing solutions and techniques, tailored to fit specific well conditions and to provide optimum stimulation per dollar cost. Acidizing treatments may be classified into three basic categories—(1) treatments in which the acid is injected uniformly into the pores and flow channels of the matrix, (2) treatments in which the acid enters natural fissures and fractures in the formation at less than fracturing pressures and (3) injection of acid into the formation at a pressure sufficient to open and extend fractures into the rock through which the acid penetrates (without the inclusion of a propping agent). TYPE 1 — MATRIX ACIDIZING This category consists of treatments in which acid solutions are injected into a homogeneous carbonate