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By N. S. Dalal, V. Castranova, K. Van Dyke, V. Vallyathan, J. H. Kang

Previously we reported crushing or grinding crystalline silica results in silica-based free radicals on the particulate surface which can generate hydroxyl radicals in aqueous solution (1). Now we find that freshly ground silica is more cytotoxic to and a more potent activator of alveolar macrophages than similarly sized aged silica. Since the United States Department of Labor estimates that over 1.25 million American workers may be exposed to freshly ground crystalline silica arid nearly 60,000 may be at risk of developing some degree of silica-based occupational lung disease, then this is hardly a trivial problem. Occupations of concern include workers who come in contact with silica including miners of soft and hard minerals, stone quarry workers, glass workers and even millers who stone grind flour. Acute silicosis is manifested by inflammation, alveolar lipo-proteinosis, and the rapid development of respiratory disability that depending on the dose of silica can produce chronic silicosis which takes 20 - 40 years to develop. It is demonstrated by the appearance of concentric hyalinized nodular lesions and progressive development of dyspnea(3). Certainly the free radicals produced on the surface of freshly ground crystalline silica play a most important role in producing the acute and chronic symptoms of silicosis. When respirable-size freshly- ground silica (0.1 -- 5 microns in diameter) enters the deep alveolar spaces in the lung and contacts an aqueous environment, hydroxyl radical are generated and cellular damage is bound to occur. We have found that freshly ground silica can cause lipid peroxidation and lysis of erythrocytes(1). The objective of this investigation was to further elucidate the enhanced toxicity of freshly ground versus aged silica. It can be deduced from the data that not only is freshly ground silica more cytotoxic to alveolar macrophages but it is a more potent stimulant of these phagocytes. However the mere characterization of toxicity is not entirely helpful if there is not a useful means to detoxify the cause of the damage. We have identified an aqueously soluble substance that can be used in high dilution to detoxify the SiO(•) and Si(•) type of free radicals. This is the organosilane known as Prosil 28 (R). We have found that coating of the freshly ground silica can effectively reduce its toxicity. The importance of this observation is that such a coating could be used with water cooled drills. This may partially detoxify silica at the point of generation of the free radical, i.e., the generation of the fresh silica dust itself. Such a coating could be used in great dilution 1:103 or 1:104. The coating would be long lasting, inexpensive and should be non-toxic because of the great dilution.

Jan 1, 1991

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By A. A. Smith, J. S. Smart

NUMEROUS investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previously.1 The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range 0 to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synthesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature were obtained by drawing the continuous cast rod to wire of 0.081-in. diameter, employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By E. P. Abrahamson II

The effect of transitiorz element bitzary solid solution additions upon the recrystallization temperature of columbium has been investigated. The elements Mn, Fe, Co, Ni, W, Re, and 0s OWY the yecystallization tempel-aturye, while Ti, V, CY, zr, Mo, Ru, Rh, Pd, Hf, Ta, W, Ir, and Pt mise it. A correlation is kloted between the rate of chatzge of recyystallization tewaperature with atomic hercent solute and the free atom electron configuration of the solute element. The work of Abrahamson and Grant1 has indicated a correlation between the free atom ground-state electron configuration and the change in brittle-ductile transition temperature per atomic percent solute in chromium base alloys. A similar correlation was observed for the change in the recrystallization temperature of iron base alloys by Abrahamson and Blakeney and Abrahamson. It was also observed that the limit of rapid change in recrystallization temperature also Correlated with the electronic configuration of the free solute atom. A further study by Abrahamson4 established the generality of the phenomenon by yielding similar results for vanadium base dilute alloys. It has been inferred that a peri- odicity might be expected with changes in the free atom electron configuration of the solvent element. This study is the third set of transition base metal systems to be studied. It is the object of this and further studies on transitional metal systems to detect any systematic variations in the observed correlation which might contribute to the understanding of the electron interactions which are evidently exhibiting themselves. PROCEDURE All alloys were made using 99.9 pct Cb with 0.030 Ta, 0.016 0, 0.0025 H, 0.003 Mo, 0.021 Fe, 0.005 C, and 0.002 N. The solute elements were 99.9 pct pure. According to the published binary phase diagrams5 and metallographic examinations at X750, all additions were in solid solution. The alloys were arc melted and remelted 6 times in the form of cubic 400-g buttons under an argon atmosphere. They were then hot forged at 1200oC to 0.6-in. diameter, annealed for 3 hr at 1200o under argon, and furnace cooled. The specimens were then machined to 0.400 -in. diameter. Grain size was checked and found to remain essentially constant at 150 i 30 grains per sq mm. The specimens were then cold swaged to 0.187-in. diameter, yielding 46 i 1 pct cold work. All alloys were chemically analyzed for the major solute. Analyses of random samples indicated that the impurity content remained at the values of the starting material. Tungsten contamination was held to 0.007 pet.

Jan 1, 1962

By P. Chiotti, J. T. Mason

Metallographic, thermal, X-ray, and vapor-pressure data were employed in establishing the Ce-Zn phase diagram. Nine compounds and three eutectics were observed. The eutectic compositions in weight percent zinc and temperatures are 10 pct and 495"C, 37 pct and 795°C, and 56 pct and 810°C. Three of the compounds, CeZn, CeZnn, and CeZne.5, melt congru-ently at 825°, 87.505°, and 980°C, respectively; the other six compounds, CeZns, CeZns.67, CeZn4.5, CeZn5.25, CeZn,, and CeZnll, decompose peritectically at 820°, 840°, 870°, 885", 960°, and 795"C, respectively. The compound CeZn5.25 is an AB5 type with a small range of composition which lies on the zinc-rich side of the 1 to 5 stoichiometry. Zinc vapor-pressure data obtained by the dewpoint method were employed in calczilating the thermodynamic properties of both the liquid alloys and solid compounds. The data for the A critical review of the information available on the Ce-Zn system up to 1960 has been given by K. Gschneidner, Jr.' Of particular interest is the work by J. schramm2 who investigated the region between 55 and 100 wt pct Zn and reported a CeZn,, compound which decomposes peritectically at 785"C, a CeZn, compound which melts congruently at 972"C, and five temperature horizontals at 79@, 817", 840", liquid alloys were fitted to the relation from which the relation was obtained by integration. In these relations F XS is the excess partial molal free energy, N is atom fraction, and the constants c and d have the values c = (-22,000 + 7.0T) and d = 6171,000 + 74.0T). Relations for the standard free energy of formation for the solid compounds were derived from the data. At 973°K the enthalpy in kilocalories per gram-atom z)aries from —11.3 for CeZnz to —8.21 for CeZn~l and the free energy in the same units varies from —7.1 joy CeZn, to -3.82 for CeZn11. and 942°C in the region between 55 and 75 wt pct Zn. No attempt was made to identify other features of the system. I. Johnson and R. yonko3 used a fused-salt cell to measure the electromotive force between pure cerium and an alloy consisting of zinc-rich liquid in equilibrium with CeZnll. Solubility data for cerium in zinc has been reported by J. Knighton et u1 .4 Johnson and Yonko give the following equa-. tions for the mole fraction of cerium in zinc and the standard free energy of formation of CeZnll:

Jan 1, 1965

By Gordon V. lewis

The Penjom gold mine treats highly preg-robbing carbonaceous ore by using relatively inexpensive gravity and hydrometallurgical methods. The mine is a joint venture between Avocet Gold Limited, a subsidiary of Avocet Mining PLC, a U.K listed mining company with interests in gold and tungsten, and the Pahang State Development Corporation (PKNP) who receive a 2% royalty. The operating team at Penjom embarked on a programme of innovation during 1998 following a realisation that almost all of the primary ore in the gold deposit was highly carbonaceous in nature. Earlier attempts at desliming and leaching the deslimed product through a normal CIL circuit had failed, and through shear necessity, the team turned to new technologies which were considered most suited to the ore characteristics indicated from pre­feasibility testwork. Between April and September, 1998, the mine introduced three key processes, which combined represent the elements of "The Penjom Process". The gravity circuit was boosted to maximise the capture of leachable sulphide and free gold from the relatively carbon free cyclone underflow stream, kerosene and diesel blanking was introduced to treat the cyclone overflow and RIL (resin-in­leach) technology utilised to replace the existing CIL (carbon-in-leach) circuit. Further experimentation with selective resin in partnership with Mintek of South Africa yielded a significant improvement to the process during 1999. Minix­Dowex resin was introduced mid year to replace a non-gold selective resin, which had been used in a flotation/batch leaching circuit for about nine months. Lower carbon levels in the feed at that stage led to the abandonment of flotation and the introduction of continuous RIL, which has been adopted as the major chemical process at the Penjom gold mine since September, 1999. Given the proven performance of the circuit to date, this process may be considered as a low cost option for the treatment of highly carbonaceous ores, particularly those which are not refractory and contain a reasonable percentage of free gold.

Jan 1, 2000

By R. W. Heins, N. Street

Recently Hiller1 reported results on the impairment of the strength of quartz glass rods through wetting, indicating that there was general agreement with the prediction of the Griffith formula in that for the liquids used the rods were weakest in water i.e. the liquid which probably had the greatest free energy of immersion. The Griffith equation predicts that the tensile stress necessary to propagate a crack of length c is where ? is the interfacial free energy, E Young's modulus. Since for a solid immersed in a liquid of surface tension ?L and contact angle 8 at the solid-liquid-gas contact, ?s - ?SL = ?L cos ? where ?s is the surface free energy of the solid. Hence comparison between ?L cos 0 and strength impairment should be possible. In a study of the usefulness of the Kuznetsov pendulum2 as a means of studying rock drillability we have determined the effects of various liquids on the pendulum hardness of Bavarian limestone. The pendulum used had diamond points (Burgess Vibro-graver), a period of 1.14 sec and a total on sample weight of 1191 g. The decline of the pendulum oscillations was recorded by a light beam on light sensitive paper carried on a kymograph. Rehbinder's expression relating hardness to amplitude attenuation as a function of time can be written In A = - (1/H) t + In Ao where A, A, = amplitude at time t and initial amplitude respectively, H = hardness parameter, and t = time. The line of best fit to the experimental points was determined using the IBM 7090 electronic computer, the computer also gave A, by extrapolation to zero time. The results for the various liquids tested are given in Table I and Fig. 1. The limestone surfaces were highly polished before testing and each reported hardness value represents the average of at least ten separate determinations of the pendulum decline curve. On each newly prepared surface the water value was again determined (also

Jan 1, 1964

State of Indiana, Department of Conservation, Division of Geology, Indianapolis, Ind. W. N Logan, State Geologist A list of the publications will be sent upon request. A series of yearly reports have been issued, with a few early exceptions, since 1869, up to and including the 41st (1916) Five of these are issued free, 18 are out of print, and the rest may be obtained at a quoted price. Beginning in 1917, the administrative reports of the State Geologist have been published in the Indiana Year Book. In 1919, the Department of Geology and Natural Resources became the Division of Geology in the Department of Conservation and separates of later reports in the Year Book are available, as follows. 3rd Report (1921), Gold in Indiana, 4th (1922), The New Albany shale, peat deposits of Indiana; 5th (1923), Petroleum conserva¬tion, 6th (1924), Conservation of natural gas; 7th (1925), Coal losses of Indiana, 10th (1928), Geological conditions in the Siosi oil field, 11th (1929), The mineral fuel resources of Indiana, 12th (1930), Oil and gas developments in 1930. (Titles of lesser interest are omitted ) The following Special Reports have been printed as publications of the Department of Conservation: Special Report 6, Kaolin of Indiana (1919), free; 21, Handbook of Indiana geology (1922), $5 to nonresidents and $3 to residents, 42, Geologic conditions in the oil fields of southwestern Indiana (1924), 75 cents to non-residents and 50 cents to residents; 55, Geology of the deep wells of Indiana (1926), $1; 75, Geology of the Silurian rocks of northern Indiana (1928), $1, cloth bound, 8125, 78, Indiana oolitic limestone map of Monroe-Owens counties (1928), $1, 79, Indiana oohtic limestone map of Lawrence County (1928), $1; 90, The geologic history of the vertebrates of Indiana (1929), $1, cloth bound, $125, 91, The ceramic materials of Indiana (1929), free, 98, The Borden (Knobstone) rocks of southern Indiana (1931), $1 25, cloth bound, $150, 101, Insoluble residue studies of Mississippian limestones in Indiana (1931), 25 cents

Jan 1, 1933

By H. R. Page, A. E. Jr Lee

A. E. LEE, JR. (author)—In addition to the paper we should like to make a few remarks. First, the seriousness of bending of the clay retort cannot be overemphasized. Not only did bending limit the length of the vessel, but it permitted corrosive fluid slags to concentrate in the belly of the retort and thus increased the possibility of boring. Bending also practically prohibited the use of cleanout machines and increased the danger of excessive fume losses by allowing furnace gases to escape around the top of the retort mouth. It will be noted that the Blackwell pottery practice places considerable emphasis on careful drying of retorts. Perhaps it is another smelter superstition, but traditionally the aging of retorts beyond a reasonable drying period has been considered important to long life. We are unable to give a good explanation of why aging should improve retorts. During the past fall in an attempt to prove a theory that the combined water in the clay decreased during aging, about 50 samples of wet retort collars were placed in a dry room when it was closed. Loss of weight, combined water and free moisture were measured each week over the 100 day drying period. The affinity of the dried retort for moisture makes difficult the accurate measurement of free water; however, there was a clearly defined free moisture change from about 12.5 pct when freshly made to about 2 pet at the end of 18 days, then a gradual loss to about 0.25 pet at 70 days and an apparent equilibrium near this figure through the 100th day. There was no appreciable change in the combined water. The change in weight of the average sample was, however, rather unusual, there being consistently a loss of weight throughout the entire 100 days. From the 63rd day on this leveled off to about 0.03 pet per week. These were small samples and certainly should have dried

Jan 1, 1950

By Ernest Darby

WHEN bronze is melted in open-flame furnaces a considerable amount of slag is formed during the melting operation. This slag may be incidental to the melting practice or it may be formed intentionally by slag-forming constituents added to the furnace charge to provide a covering for the melted metal. When this slag is removed from the furnace, it contains, in addition to the free metal carried with it by the skimming operation, a considerable amount of metal as oxide either combined or mechanically mixed with it. By the usual crushing and washing methods this metallic oxide generally goes to the tailings pile, so diluted by other foundry waste that its recovery is economically impossible. If this furnace slag is not mixed with other foundry waste, practically all of the metal oxide as well as the free metal may be recovered by some form of smelting operation. The first side of the problem to be considered is the amount of slag produced. It may not be true that the majority of foundries have no record of the amount of slag made, but it is certainly true that a very great many either have no record or pay little attention to it. Usually the collection of furnace slag for one normal week's run will be sufficient to determine the advisability of its being handled in a different manner from the crushing and concentrating generally employed. If a large representative sample of the accumulation is crushed and concentrated and the recovery compared with the results of a careful assay, it will be found that a large percentage of the total metal content was lost in the washing process. The percentage of loss will be greater than the metallic oxide content, as some free metal in extremely fine particles always is carried away in grains of slag. From such a comparison, it may be determined whether or not the slag should be melted, sold or treated as before. An example of an actual test of this kind is given below.

Jan 1, 1928

By Ionel Gardescu

IN connection with some of the experiments carried out by the writer on the behavior of gas and oil in a sand reservoir,1 an interesting phenomenon was observed which may throw some new light on the problem of recovery of oil from a natural reservoir. The experiments are intended to show the effect of the surface area of the occluded gas masses, originally present in a reservoir, on the further evolution of gas from the oil and its consequent effect upon the rate of production of oil. The apparatus used in the experimental work is shown in Fig. 1. It consists primarily of a sand reservoir R and a displacement chamber D, which is used to induce small variations in volume. The reservoir and displacement chamber form a unit, and a lowering of the plunger D is equivalent to increasing the volume occupied by the oil and gas in the reservoir. The reservoir was first filled with dead oil and maintained under pressure until it was ascertained that most of the free gas had gone into solution. The volume of free gas present in the reservoir was computed from the coefficient of compressibility of the fluids by means of the dis-placement chamber D, reading to 0.005 c.c. and a special gage J reading to 0.02 lb. per sq. in. The oil was saturated with gas under pressure in reservoir S by circulating the oil for a long period of time through the gear pump B. Subsequently, the saturated oil was circulated through the sand reservoir following the circuit S6, B, S5, R4, the sand reservoir R, R1, R2, F4, F1, back to reservoir S. In the following experiments the sand reservoir R was filled with gas-saturated oil at a pressure of 415 lb. per sq. in. with no free gas present. This was ascertained by. closing off all the outlet valves, and determining the coefficient of compressibility of the system by means of the dis-placement chamber D.

Jan 1, 1932

By M. A. Rigdon, R. E. Grace

The dissociation of cupric oxide to cuprous oxide and oxygen was studied with a microbalmce technique at 700" to 750°C. In this temperature range the dissociation pressure of the reaction 2CuO= Cu2O + 1/2 O2 was: The theory of near-equilibriwm reaction rates predicts a linear relationship between reaction rate and the Gibbs free-energy change for small values of AF/RT. This correlation is found to be valid for AF/RT = -0.1 or approximately 200 cal per mole away from equilibrium. THE theory of reaction rates near equilibrium as developed from classical thermodynamics suggests a small range of linear behavior between the overall reaction rate and the free-energy change accompanying the process. The extent of this linear correlation is generally unknown, even to the order of magnitude. The idea of linearity is also found in the formal mathematics of coupled transport phenomena, e.g., chemical diffusion, thermal diffusion, thermoelectricity, and so forth. The linear array of forces and fluxes which leads to various main and cross coefficients is predicated upon linearity between reaction rates and the bulk thermodynamics which govern the process. The general case in reaction kinetics is well-known: the magnitude of the free-energy change does not cor- relate with observed reaction kinetics, irrespective of whether the process occurs by diffusion or chemical reaction or both. The real need is to investigate specific reaction paths near equilibrium in order to learn of the limitations in attempting to correlate reaction rates and thermodynamics. It is the main purpose of this paper to examine the dissociation kinetics of cupric oxide under conditions of known driving force where the dissociation process is likely to occur by chemical reaction. A secondary objective is to obtain equilibrium data for the CuO-Cu20-O2 system. In a prior paper Edmiston and race' investigated reduction kinetics of wustite in H2-H2O gas mixtures. The present study was carried out in oxygen according to the following reaction:

Jan 1, 1969

By Ernest Darby

WHEN bronze is melted in open-flame furnaces a considerable amount of slag is formed during the melting operation. This slag may be incidental to the melting practice or it may be formed intentionally by slag-forming constituents added to the furnace charge to provide a covering for the melted metal. When this slag is removed from the furnace, it contains, in addition to the free metal carried with it by the skimming operation, a considerable amount of metal as oxide either combined or mechanically mixed with it. By the usual crushing and washing methods this metallic oxide generally goes to the tailings pile, so diluted by other foundry waste that its recovery is economically impossible. If this furnace slag is not mixed with other foundry waste, practically all of the metal oxide as well as the free metal may be recovered by some form of smelting operation. The first side of the problem to be considered is the amount of slag produced. It may not be true that the majority of foundries have no record of the amount of slag made, but it is certainly true that a very great many either have no record or pay little attention to it. Usually the collection of furnace slag for one normal week's run will be sufficient to determine the advisability of its being handled in a different manner from the crushing and concentrating generally employed. If a large representative sample of the accumulation is crushed and concentrated and the recovery compared with the results of a careful assay, it will be found that a large percentage of the total metal content was lost in the washing process. The percentage of loss will be greater than the metallic oxide content, as some free metal in extremely fine particles always is carried away in grains of slag: From such a comparison, it may be determined whether or not the slag should be melted, sold or treated as before. An example of an actual test of this kind is given below.

Jan 1, 1928

By N. H. Murlenberg, T. M. Drown

It is often a tedious matter to get a solution of pig iron or steel, for the determination of phosphorus, which is absolutely free from silica. Where pig iron rich in silicon is dissolved in hydrochloric or nitric acid in the usual procedure, it is necessary, not only to evaporate the solution to complete dry ness, but to heat the dry residue for some beam in an air-bath to a temperature of about 120° C. The oxide of iron is thus rendered insoluble in nitric acid, and is only slowly dissolved by hydrochloric acid. In the method of determining silicon by nitric and sulphuric acid, described in the Transactions of the Institute, Vol. VII, page 346, arid Vol. VIII, page 508, we obtain in one or two hours a solution of the iron in the form of ferric sulphate entirely free from silica, and containing free sulphuric acid. It occurred to Us that this solution might be made available for the determination of the phosphorus by the molybdate method. The following experiments mere tried with unsatisfactory results. 1st. The iron was precipitated by ammonia, the precipitate filtered, washed, and dissolved in nitric acid. 2d. The iron was precipitated as basic acetate and dissolved in nitric acid. 3d. The solution was neutralized by ammonia, and nitric acid added in small excess. In all these cases the phosphorus obtained by precipitating by ammonium molybdate and magnesia-mixture was too low. The following method was then tried with success. The filtrate from the silica and graphite was evaporated to small bulk and heated in a porcelain dish on a sand-bath. until fumes of sulphuric acid ceased to escape. The dry residue was taken up with dilute nitric acid and the solution precipitated by ammonium molyldate. The phosphorus was weighed as magnesium pyrophosphate. The results were satisfactory. To save time, the original solution of the iron in nitric and sulphuric acids was evaporated to dryness and heated as before until

Jan 1, 1882

By N. H. Muhlenberg

IT is often a tedious matter to get a solution of pig iron or steel, for the determination of phosphorus, which is absolutely free from silica. Where pig iron rich in silicon is dissolved in hydrochloric or nitric acid in the usual procedure, it is necessary, not only to evaporate the solution to complete dryness, but to heat the dry residue for some hours in an air-bath to a temperature of about 120° C. The oxide of iron is thus rendered insoluble in nitric acid, and is only slowly dissolved by hydrochloric acid. In the method of determining silicon by nitric and sulphuric acid, described in the Transactions of the Institute, Vol. VII, page 346, and Vol. VIII, page 508, we obtain in one or two hours a solution of the iron in the form of ferric sulphate entirely free from silica, and containing free sulphuric acid. It occurred to us that this solution might be made available for the determination of the phosphorus by the molybdate method. The following experiments were tried with unsatisfactory results. 1st. The iron was precipitated by ammonia, the precipitate filtered, washed, and dissolved in nitric acid. 2d. The iron was precipitated as basic acetate and dissolved in nitric acid. 3d. The solution was neutralized by ammonia, and nitric acid added in small excess. In all these cases the phosphorus obtained by precipitating by ammonium molybdate and magnesia-mixture was too low. The following method was then tried with success. The filtrate from the silica and graphite was evaporated to small bulk and heated in a porcelain dish on a sand-bath, until fumes of sulphuric acid ceased to escape. The dry residue was taken up with dilute nitric acid and the solution precipitated by ammonium molyhdate. The phosphorus was weighed as magnesium pyrophosphate. The results were satisfactory. To save time, the original solution of the iron in nitric and sulphuric acids was evaporated to dryness and heated as before until

Jan 1, 1882

By C. F. Austin, J. K. Pringle

In view of the many large differences in structure and physical properties between metals, plastics, and most rock materials, a continuing experimental petrodynamics program has been established at the U. S. Naval Ordnance Test Station. Part of this program has been to test the concepts of scabbing and corner fracturing in a typical coarse-grained rock. The results of this experimental program have shown very interesting differences between the formation of fractures in rock and the formation of fractures in other materials such as metals and plastics which are often used as models for rock behavior studies. The gross behavior of coarse-grained brittle solids subjected to impulsive loading has undergone abundant empirical investigation by mining organizations and by mineral research agencies. However, the fundamental response of coarse-grained brittle solids to impulsive loading has received little detailed study in recent years. The various organizations and agencies interested in rock-like brittle materials have broadly applied the stress wave interaction concepts of the impulsive failure of metallic samples to the behavior of granular brittle materials 1,2,3,4,5,6 Using the metallic sample approach for stress wave induced fracturing, an understanding of the fracture behavior of brittle materials which perhaps is not always appropriate has been established in the open literature. An excellent summary of the metallic sample approach is provided by ref. 7 which summarizes the general beliefs prevalent at present regarding the impulsive behavior of brittle solids: "In the blasting process, rock breakage occurs primarily from tensile slabbing, beginning at a free face and proceeding back toward the explosive charge. The tensile waves formed by the reflection of incident compressive waves from two or more free faces will collide in the rock, resulting in large localized tensile stresses. Fractures formed by the interaction of these tensile stresses begin at the apex of the free face planes and progress back into the rock as shown...."

Jan 1, 1964