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By C. B. Clark, W. H. Bruckner

Since the end of World War II interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Mun-roe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research On shaped explosive charges, the following have been established concerning cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the 'One as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfmnance and more obtuse angles require thicker walls for the same base diameter' 2. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, tensile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45° cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

By C. A. Stewart

PAGE. I. Introduction............ 241 II. Location. TopoGRaphy. and History....... 243 III. DescRiption of the Rocks......... 245 1. Altered Sediments.......... 245 2. Alaskite........... 246 3. Alaskite.Porphyry.....255 4. Quartz Dikes........... 257 5. Biotite.Granite.......... 256 6. Quartz.Porphyryl......... 260 7. Andesite........... 262 8. Miscellaneous Dikes......... 263 IV. Age oF the Rocks and Comparison with other Localities.. 263 V. AlteRation............ 265 1. Sericitization........... 265 2. Silicification........... 266 VI. StRuctuRes........267 1. Dip of the Limestone......... 267 2. Faulting........... 267 VII. Contact - metamorhism,.......... 269 1. Endomorphism.......... 269 2. Exomorphism......... 271 Recrystallization and Loss of Color...... 271 New ,Minerals.......... 272 Addition of Material........ 274 Volume.Changes.... 276 Locus of Metamorhism........ 277 Method of Precipitation.........278 VIII. ORe-Deposits............ 278 1. Contact-Metamorphic Copper.Ores,..... 279 General..........279 Shape and Distribution........ 279 Minerals........... 281 Secondary Enrichment........ 282 2. Disseminated Copper.Ores........ 283 3. Origin of the Copper.Orcs........ 284 4. Lead-Silver Ores.......... 287 IX. Bibliography............ 288

Jan 1, 1913

By L. H. Levenson, Charles S. Barrett

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By Charles S. Barrett, L. H. Levenson

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —('grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By D. M. Hausen

This study identifies and describes various crystalline phases of the V205-Na20 system, and relates their properties to metallurgical aspects of vanadium production. Phase equilibria and stability ranges of sodium vanadate phases of varying molar ratios of Na20/V205 were investigated in a variety of plant products, ranging from fused "black cakes" (V20 melts) to "salt roast" calcines. Crystalline compounds, Including vanadium pentoxide, V205; sodium vanadyl vanadate, 6 phase, Na2O.V2O5.5V2O5; sodium vanadyl vanadate, y phase, 5Na20.V204.12V205; sodium metavanadate, Na20 .V 05; sodium pyrovanadate , 2Na20 .V205; and sodium orthovanadate, 4Na20.~2~5, have been characterized with the aid of X-ray diffraction patterns, infrared spectra, and optical properties in addition to chemical analyses, as a guide to mineralogical "troubleshooting" of plant problems and processes in vanadium pyro- and hydrometallurgy.

Jan 1, 1984

By T. Egleston

THE materials containing copper which are refined in the United States, are, for the most part, the native, coppers of Lake Superior. Until quite recently but little pig copper was made for sale, and that came principally from the pure sulphurous ores of New England and the South, and was generally sold to refineries not far from the ore furnaces. A small amount found its way into the market which was produced either as the by-product of the treatment of gold and silver ores, or as the result of the treatment of impure copper ores; but both these grades, on account of the impurities they contained, were looked on with suspicion, and were not sought for. All the grapes of pig copper are sold by the unit of copper contents, a great reduction being made in the price when impurities are present. There are at the present time only three works which treat native copper, the two of the Detroit and Lake Superior Copper Company, and the works of C. G. Hussey & Co., in Pittsburgh. There are a few works which smelt sulphurous ores and refine their pig; besides these there are a few small works where pig copper is refined only. Some of these purchase black copper, refine scrap, or simply refine such grades of ingot copper as are found in the market, but mostly that from Lake; Superior, for the purpose of getting it into such shapes that can be handled commercially to advantage, such as in making large plates or high grades of wire for electrical purposes. A number of such works are situated in the Naugatuek Valley and elsewhere in New England. The recent discovery, of valuable ores in Arizona makes it probable that within a few years the refining of copper in the United States will make great developments. Up to the time of the discovery of the mines on Lake Superior, only a very small quantity of native copper had ever been found, not sufficient to justify the erection of works for its special treatment. It had, besides, never been found in very Large masses, so that the discovery of great-blocks of it presented serious difficulties, not only in mining it,† but in bringing it into a merchantable condition. It seemed a very simple process to melt these large masses, * Road at the Lake Superior Meeting, August, 1880. †Transactions American Institute Mining Engineers, vol. vi, page 2S2.

Jan 1, 1881

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By R. M. Brick

THE etched microstructures of cold-worked alpha brasses, after reduc-tions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonomously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {111}, in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson5 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into sym-metry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By R. S. Busk, R. F. Marande

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By R. F. Marande, R. S. Busk

The magnesium-aluminum-zinc 'system contains most of the magnesium-base alloys used commercially, although in practice the ternary alloys are usually modified by the addition of a small amount of manganese. Table I contains the magnesium-base commercial sand-casting alloys most widely used throughout the world, together with their typical tensile properties. These alloys may be regarded as a single family of varying aluminum and zinc content, disregarding manganese. A concise means of presenting data for them is by means of iso-property lines plotted on triangular coordinate paper. Constitutional, casting, and mechanical properties are presented in this manner. The data are given with the obiect of providing reference material, and to aid in the choice of a commercial alloy to serve a particular purpose. Detailed, critical analysis of the commercial alloys has been covered in a previous paper.' All alloys reported were made in rj-lb. melts, superheated to r700°F. for 15 min., cooled to r400°F. and poured in sand molds. The test bars produced had a 1/2-in. reduced section and were about 6 in. long. Except for the data represented in Figs. I and 3 the alloys used were of commercial purity and contained 0.1 to 0.2 per cent Mn in addition to the aluminum and zinc. Constitutional Data Under the heading of Constitutional Data are included all known data on con-

Jan 1, 1946

By T. D. Thomas

CONTENTS PAGE T. D. Thomas-Misfires in Anthracite Coal Mines 3 W. H. Forbes-Misfires in Bituminous Coal Mines 12 A. W. Worthington-Misfires in Non-metallic Mining (Limestone) 18 Misfires in Anthracite Coal Mines BY T. D. THOMAS, * LANSFORD, PA. (New York Meeting, February, 1929) IN THIS paper, major attention is given to misfires in mines where electric multiple shot-firing is the system used. Misfires are sometimes caused by one action or condition and at other times by a combination of two or more. They may be divided into two classes: (1) those caused by workers in the mines, (2) mechanical or manufacturer's causes. The second cause will be discussed first.

Jan 1, 1929

By R. D. Groves, G. M. Potter, T. H. Jeffers

Experiments on ammonium carbonate leaching of native copper ores crushed to 1-inch size showed that in 30 days 55 percent of the copper was extracted from 0.7 percent copper conglomerate-type ore, and 85 percent was extracted from 2.1 percent copper amygdaloid-type ore. Cupric ions were not necessary to initiate leaching, and dilute solution containing only 2.2 grams per liter NH3 and 1.9 grams CO, was a suitable solvent. Copper was recovered from the leach liquor by solvent extraction and electrolysis of the strip solution. Cyclic testing of the leach-solvent extraction-electrolytic procedure is in progress on a 6-ton charge of minus 12-inch conglomerate-type ore assaying 2.2 percent copper. Oxygen is metered to the closed leach vessel as required by the leaching reaction. Initial copper dissolution was much slower than from minus 1-inch ore, but the leaching rate then markedly improved.

Jan 1, 1974

By Zay Jeffries

This paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.l The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the At transformations. 4. The grain-size refining of steel and iron is brought about by the combined effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation products do cst inherit their grain size from the austenite on cooling through the transformation range nor does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. In this instance small austenite grains may form very large ferrite grains on cooling through Arg.

Jan 1, 1918

By E. W. Dewing

ROLIN1 in 1961 published a phase diagram for the CaF2-Na3AIF6 system in which substantial (-20 wt pct) solid solubility of CaF2 in Na3A1F6 at the eutectic temperature (945°C) was indicated. The evidence was that the halt in cooling curves associated with the eutectic was lowered progressively on the Na3AlF6 side. H olm2 has recently confirmed the experimental fact, but attributes it to evaporation losses shifting the composition into the ternary NaF-CaF2-Na3A1F6 system with a consequent lowering of the eutectic temperature

Jan 1, 1970

By Chas. H. Behre, Arbiter. Nathaniel

Two outstanding factors characterize most undertakings in the mineral industries: (1) mineral deposits are not equally distributed over the earth but are localized by natural processes, and (2) the mineral industries are largely based upon wasting assets. Neither of these factors is invariably true, for a few mineral materials, such as water, are essentially world-wide and others are replaced periodically by processes not unlike crop production. Indeed, with some, such as the salts in the sea, the supply is cyclic in short or long periods, whereas others, like water, though locally or periodically in short supply, are essentially inexhaustible. But to the extent that most minerals are limited to certain areas and are "permanently" consumed, any industry founded upon them, by implication, demands great care in planning for the most effective extraction-the essence of wise and conservative expenditure. Several less unusual yet also truly fundamental factors in the economics of the mineral industry are those involving (1) the various kinds and properties of mineral materials, which influence their use; (2) their geo- logic and geographic availability; and (3) the techniques unique to their discovery, exploration, and utilization. This chapter is designed primarily as a brief background for later ones and as a summary of the several un- usual or at least special factors and of their effect upon the economics of the mineral industry. The social and political and especially the economic aspects of the industry are the main subjects of this volume and are dealt with in extended fashion in subsequent chapters. Fundamental Characteristics of Mineral Deposits DEFINITIONS Minerals are naturally occurring compounds of nonliving matter, each technically defined as having (1) a chemical composition that may vary

Jan 1, 1959

By Yingchang Tsenshan Wang

UUIN L&SS 1» Paqb I. Introduction........................................................658 1. Subject and Scope...............................................658 2. Acknowledgments...............................................659 3. Review of Previous Work........................................659 Field Data...................................................659 Experiment.a1 Data............................................662 4. Plan of Present Investigation.....................................662 Method of General Procedure...................................663 I1. Experimental Work..................................................663 A. The Solution of Sphalerite..............................:........663 1. The Solvent Effect of Iron Sulphates upon Sphalerite...........663 2. The Solubility of Sphalerite in Salt Solutions of Silver, Copper and Lead...............................................668 B. Formation of Zinc Carbonates....................................674 3. The Reactions of Carbonates and Bicarbonates With Solutions of Zinc Salts............................................674 4. The Reaction of Zinc.Sulphate Solution With Limestones.......684 C. Peculiar Conditions Affectitig the Formation of Zinc Silicate (calamine) and Zinc Carbonate (smithsonite)..........................686 5a. The Effect of Carbon Dioxide Upon the Basic Silicate and the Carbonates of Zinc in Water, and Its Bearing Upon the Conditions of Theii Precipitation..............................686 5b. The Reactions of Solutions of Soluble Silicate With calamine and Smithsonite in Solution in Presence of Carbon Dioxide..689 6. The Reactions of a Mixture of Hydroxide and Silicate of Sodium with a Dilute Solution of Zinc Sulphate...................691 D. High-Temperature Methods.....................................692 7a. The Influence of Temperature on the Formation of Calamine..692 7b. Possible Effect of Heat on Calamine and Srnithsonite.........697 E. Summary of the Experimental Work..............................698 III. Petrographic Work....................................................700 1. The Occurrence of Sphalerite in Limestones or in Cherts............701 Summary of the Blende in Limestones and in Cherts.............7432 2. The Partially Altered Sphalerite and the Oxidation Products........702 a. Smithsonite with Blende....................................702 b. Calamine with Blende......................................703 c. Smithsonite and Calamine..................................703 d. Summary on the Partially Altered Sphalerite and Its Oxidation Products..............................................704 IV. Concl~~siom ........................................................-705 V. Microphotographs and Photographs with Their Explanations.............705

Jan 1, 1916

By Michael H. Kuryla, Galen H. Clevenger

Some years after Nobel made his epoch-making contribution to the knowledge of high explosives, Sprengell described a new class of detonating explosives consisting of mixtures, made immediately before use, of an oxidizing agent and a combustible substance.2 The novel feature of the Sprengel explosives is that the constituents alone are non-explosive during manufacture, storage and transport. Despite this advantage, and although some of these have been used in important work, they are now little used, possibly on account of the greater inconvenience to the user, compared with explosives supplied by the manufacturer in final form. Liquid-oxygen explosives are a type of Sprengel explosive in that the oxidizing agent (liquid oxygen) and the combustible substance or substances (solid carbonaceous matter alone or in combination with liquid hydrocarbons or even metallic powders and, at times inert absorbents) are brought together immediately before use. The components separately are non-explosive. The possibility of using liquid oxygen as one of the components of an explosive was perhaps first suggested by Sprengel, who stated that the beau ideal of a detonating explosive was a mixture of eight parts of liquid oxygen with one part of liquid hydrogen. Although the liquefaction of air3 had been accomplished in the laboratory as early

Jan 1, 1923

By Michael H. Kuryla, Galen H. Clevenger

Some years after Nobel made his epoch-making contribution to the knowledge of high explosives, Sprengell described a new class of detonating explosives consisting of mixtures, made immediately before use, of an oxidizing agent and a combustible substance.2 The novel feature of the Sprengel explosives is that the constituents alone are non-explosive during manufacture, storage and transport. Despite this advantage, and although some of these have been used in important work, they are now little used, possibly on account of the greater inconvenience to the user, compared with explosives supplied by the manufacturer in final form. Liquid-oxygen explosives are a type of Sprengel explosive in that the oxidizing agent (liquid oxygen) and the combustible substance or substances (solid carbonaceous matter alone or in combination with liquid hydrocarbons or even metallic powders and, at times inert absorbents) are brought together immediately before use. The components separately are non-explosive. The possibility of using liquid oxygen as one of the components of an explosive was perhaps first suggested by Sprengel, who stated that the beau ideal of a detonating explosive was a mixture of eight parts of liquid oxygen with one part of liquid hydrogen. Although the liquefaction of air3 had been accomplished in the laboratory as early

Jan 1, 1923

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965