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By H. F. Moore

Jan 1, 1936

By B. A. Wilcox, A. H. Clauer

The tensile and creep deformation characteristics of fiber reinforced composites have been studied, primarily at room temperature. The matrix was an alloy of Mg-14 wt pct Li-1 wt pct Al (LA141A alloy) and the reinforcing fiber consisted of continuous wires of a high strength precipitation hardening stainless steel (AFC-77 alloy). The ultimate tensile strength and strength-to-density ratio of composites were much improved over that of the mmix, both at room ternperatwe and up to 200°C. Creep studies at room temperature revealed logarithmic weep behavior for wires and composites and steady state creep for the nonreinforced matrix. It was concluded that creep of the fibers controlled composite creep. The instantaneous logarithmic weep rate of the composite, 6, was related to the average tensile stress on the fibers, where n = 3.4. Mg-Li alloys are the lightest structural metals commercially available, e.g., the alloy LA141A (Mg-14 wt pct Li-1 wt pct Al) is 27 pct less dense than beryllium Although Mg-Li alloys have moderate tensile strengths at normal strain rates and ambient temperature, their creep strength is relatively poor, even at room temperature. Reinforcement by fibers offers a means of increasing the tensile strength as well as overcoming the limitations of low creep strength. With a proper choice of reinforcing filament, composites could be designed with higher strength-to-density and modulus-to-density ratios than the matrix alloy. This communication reports a study on the tensile and creep characteristics of alloy LA141A reinforced with continuous wires of a high-strength precipitation hardening stainless steel (AFC-77 alloy). The matrix has a bcc structure, with possible precipitates of AlLi and MgLi2A1,3 and is ductile at room temperature Stainless steel wire was chosen as the -reinforcing filament since previous work at Battelle4 showed that a good bond between wire and matrix could be produced in this system. For all volume fractions of reinforcing wire, the theoretical composite strength-to-density ratio is greater than that of the matrix and the modulus-to-density ratio is somewhat lower than that of the matrix. EXPERIMENTAL PROCEDURES The 0.004-in. diam AFC-77 wire was obtained from two suppliers: National-Standard Co.* and Crucible 0.13 Si, 0.18 V, 0.011 P, 0.012 S, balance Fe. In the as-received condition, wires from both sources had room-temperature ultimate tensile strengths of 585,000 to 590,000 psi with approximately 2 pct total elongation and 40 pct reduction in area. Composite preparation was accomplished by the vacuum infiltration technique. This involved placing the continuous wires in a mild steel tube (1/8-in. ID), capping one end of the tube with a sheet of the matrix alloy, and evacuating the other end of the tube. When the capped end was placed in a crucible of the molten matrix alloy and held for 31/2 min at 70O°C, the liquid metal was drawn up the tube approximately 7 to 8 in. A cross-sectional view of a typical composite is shown in Fig. 1. This preparation technique promoted excellent bonding between the matrix and wires, and porosity was rarely observed. Test specimens for both creep and tension studies were prepared by machining off the steel tube. Tensile tests on the wires and composite specimens were made in an Instron using a cross-head speed of 0.01 in. per min. The composite specimens had no reduced section and were held in self-tightening grooved serrated grips. Most of the specimens broke in the effective 1-in. gage section. Even though several tests fractured in the grip section, their ultimate strengths were essentially the same as those of specimens which fractured in the gage section. Creep specimens of the composite were gripped in a similar manner, and

Jan 1, 1970

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By Donald M. D. Stuart

It gives me great pleasure to accept the invitation I had the honor of receiving through the Secretary of the Institute, to reply to the criticisms made in discussion of the theory advanced in my work entitled, Coal-Dust an Explosive Agent; and to lay before the Institute a further statement of the views which investigations have led me to form upon this subject,

Jan 1, 1897

By I. Iwasaki, K. Adam

The oxidation behaviors of simple and complex chloride systems of copper, iron, nickel, cobalt, and manganese in a stream of oxygen were investigated using a thermogravimetric analysis technique. Their reaction mechanisms are discussed from stoichiometry, thermodynamic feasibility, and X-ray diffraction analysis of reaction products. The results are used to determine an optimum operating temperature of the selective oxidation step in a chlorination process for producing nonferrous metal chlorides, elemental sulfur, and ferric oxide from copper-nickel sulfide flotation concentrates.

Jan 1, 1985

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

By PAUL P. ZElGLER

Rapid growth of the aluminum industry continued through 1948 with an acute shortage of the metal in all forms marking the year. Estimates based on shipments made during the first nine months indicate that, in 1948, the industry shipped more than two billion pounds of aluminum products or roughly four times the amount shipped in the greatest peacetime year prior to the war. The rapid expansion of the aluminum industry is particularly reflected in the production of sheet. Last year, the industry as a whole shipped an estimated 40 per cent more sheet than was produced in the peak war year of 1944.

Jan 1, 1949

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By B. H. Bergstram, C. L. Sollenberger

When glass spheres are crushed by slow compression loading, the outer lune-shaped fragments resulting from the fracture consistently fly outward at high velocity. About 45 pct of the strain energy fed into the sphere-platen system reappears in the form of the kinetic energy possessed by these fragments. These measurements were obtained from high-speed photographs. This kinetic energy can be utilized for addtional comminution if the fragments are allowed to impact against a suitable structure. Comminution theory has advanced considerably in recent years by the study of this unit operation under laboratory conditions. Some of the parameters have been isolated, but the experimental measurements of the pertinent quantities, such as energy, particle size, etc., are still only made prior to and after the conclusion of a fracture sequence. The catastrophic fracture process itself has not been adequately studied from a comminution point of view. It has recently been suggested by Gilvarry that the fragments which result from the free crushing of a single glass sphere by slow compression contain a considerable amount of kinetic energy after fracture. This kinetic energy, if properly directed, possibly can be partially utilized to cause additional fracture. In this paper a hypothesis will be presented which suggests that this kinetic energy is necessarily present and that its dissipation is the process by which a large part of the thermal energy imparted to the crushed product is generated. Evidence supporting the existence of kinetic energy and its utilization for secondary fracture will also be presented. THEORETICAL A previous paper4 has shown that the load-deformation curve of a system composed of an elastic sphere gripped by a pair of parallel platens, can be predicted by a consideration of the theories of Hertz as summarized by Timoshenko.' The deformation A, of one half of the system is given by which states that the deformation is a function of the mutually applied load, P, the radius of the sphere, R; and the respective physical properties of Poisson's ratio, v, and Young's modulus of elasticity, Y. The shape of experimental load-deformation curves conform to this relationship. The energy input to the sphere-platen system, can be predicted from the integral of the load acting through the appropriate distance, dA. Since dA can be evaluated in terms of P from the derivative of Eq. 1, this integral can be integrated between limits of 0 and P. The test sphere, however, is loaded at not one but at two points of contact, i.e., at both ends of a diameter, and hence the total energy input, E, is twice the energy input at each end, or The energy input to the system calculated from this equation corresponds to the energy computed from the measured area under the load-deformation curve. Timoshenko, considering the impact of two perfectly elastic spheres, has shown that the inter-penetration distance A is given by - m f (D (^ * ^t w as modified for the special case where one sphere is of infinite radius, i.e., its surface is a plane; where M is the mass of the finite sphere of radius R, and V is the velocity of approach at the start of an impact and also equals the final velocity of separation for perfectly elastic bodies. Because A is also a function of the load and the elastic properties, as shown in Eq. 1, the velocity, V, can also be calculated in terms of the elastic properties and maximum load, P, or

Jan 1, 1961

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

Jan 4, 1951

By V. W. Bihlman, H. M. Williams

In the construction of internal-combustion engines, the cooling of the combustion chamber and pistons is of great importance. In certain types of engines, the adequate dissipation of heat from the bearings is also important. One of the important factors affecting heat dissipation from these parts is the thermal conductivity of the material used. A search of the technical literature shows that, in general, the thermal conductivity of the elements1 has been determined accurately by a number of investigators. The data on the industrial alloys are, however, meager. For an investigation of these alloys, the thermal-conductivity apparatus described in this paper has been constructed at the laboratory of the General Motors Research Corporation. It is desirable that an apparatus for work of this nature should give fair accuracy of results with a convenient form of specimen and a reasonable rapidity of operation. A summary of the different methods of determining thermal conductivity is given in the first volume of the " Dictionary of Applied Physics," pages 429 and 470. The method selected as best satisfying these conditions is that of Griffith, on page 443, with the addition of a guard ring similar in principle to the method used by Berget (P. 445). Briefly, the method consists of heating one end of a bar T, Fig. 1, electrically, measuring the amount of heat transmitted through the bar by a flow calorimeter J fastened to the other end, and measuring the temperature gradient along the bar. To compensate for the loss of heat laterally, the test bar is surrounded by a guard ring E, in the form of a steel pipe, which is electrically heated at the bottom and cooled at the top with a

Jan 1, 1923

By V. W. Bihlman, H. M. Williams

In the construction of internal-combustion engines, the cooling of the combustion chamber and pistons is of great importance. In certain types of engines, the adequate dissipation of heat from the bearings is also important. One of the important factors affecting heat dissipation from these parts is the thermal conductivity of the material used. A search of the technical literature shows that, in general, the thermal conductivity of the elements1 has been determined accurately by a number of investigators. The data on the industrial alloys are, however, meager. For an investigation of these alloys, the thermal-conductivity apparatus described in this paper has been constructed at the laboratory of the General Motors Research Corporation. It is desirable that an apparatus for work of this nature should give fair accuracy of results with a convenient form of specimen and a reasonable rapidity of operation. A summary of the different methods of determining thermal conductivity is given in the first volume of the " Dictionary of Applied Physics," pages 429 and 470. The method selected as best satisfying these conditions is that of Griffith, on page 443, with the addition of a guard ring similar in principle to the method used by Berget (P. 445). Briefly, the method consists of heating one end of a bar T, Fig. 1, electrically, measuring the amount of heat transmitted through the bar by a flow calorimeter J fastened to the other end, and measuring the temperature gradient along the bar. To compensate for the loss of heat laterally, the test bar is surrounded by a guard ring E, in the form of a steel pipe, which is electrically heated at the bottom and cooled at the top with a

Jan 1, 1923

By Philip D. Wilson

OF all the metals in the war program the demand for and the production of magnesium have increased percentagewise the most. In the prewar year 1939 the production was 3350 tons. The war program, twice expanded, now provides for nearly one hundred times that amount annually. The goal announced by the War Production Board in February 1942 was 362,500 tons per year. Be- cause of the development during the year of satisfactory types of incendiary bombs other than magnesium this objective has been somewhat reduced but the capacity of the plants already built or under construction will be huge. The Aluminum and Magnesium Division of the W.P.B. has had the responsibility of planning and implementing this expansion and of providing fabricating facilities as well for this greatly increased tonnage of magnesium ingot.

Jan 1, 1943

By M. A. Goudie

The deposits occur in a large salt basin of Middle Devonian age. The potash, the final deposit in the salt basin, results from several interrupted cycles of evaporation and dessication. The deposits are extensive, and, at first glance, relatively undisturbed. With more and more wells being drilled, it has now become evident that salt solution has played a large part in changing the original deposits, resulting in some cases in partial to complete removal of the potash and the underlying halite. The most dominant factor in the removal of salt by solution appears to have been tectonic movement and consequent faulting, probably of relatively minor dimensions but of major importance. Evidence which indicates the tilting of the evaporite basin to the north and northwest is shown by the changing pattern of the basin during succeeding eras of potash deposition. The potash minerals of most importance economically are sylvite and carnallite. Reserve calculations indicate that 6.4 billion tons of recoverable high grade potash in K2O equivalent exist in the basin. The Devonian salt basin, which contains the Saskatchewan potash deposits, extends from just east of the foothills in Alberta, north as far as the Peace River area, across Saskatchewan and into Manitoba as far east as Range 10 west of the First Meridian and south into Montana and North Dakota (Fig. 1). The basin is closed everywhere except to the northwest. The known potash deposits are confined almost entirely to the Province of Saskatchewan, with the exception of a small area in western Manitoba bordering the Saskatchewan boundary. The following discussion will concern only the Saskatchewan part of the basin. The evaporite series in the basin is defined as the Prairie Evaporite Formation of the Elk Point Group, of Middle Devonian age. Recent work done by potassium-argon dating methods has indicated an Upper Middle Devonian (Givetian) age of from 285 to 347 million years for the potash. The Elk Point Group consists in ascending order of the Ashern, Winnipegosis, and Prairie Evaporite Formations. The Ashern formation, with an average thickness of 30 ft, sometimes called the Third Red Bed, consists of dolomitic shales and shaly dolomites. The Winnipegosis, is a reef-type dolomite, usually with good porosity, and in many cases oil-staining, although to date no production has been obtained. The thickness varies from 50 to 250 ft. The Prairie Evaporite formation, varying from 0 to 600 ft in thickness, consists of halite with interbedded anhydrite and shale, with considerable amounts of potassium salts in the upper part of the formation. The potassium salts are chiefly chlorides, although very minor occurrences of sulfates have been re- ported. The anhydrite beds do not appear to be continuous, although generally one or two bands of anhydrite underlie the lowest potash zone and are used as marker horizons. The shale occurs as seams interbedded with the salts, as large irregular inclusions in the salts and as very fine particles in intimate mixture with the salts. The Prairie Evaporite Formation is overlain by the Second Red Bed member, the Dawson Bay Formation and the First Red Bed Member of the Manitoba Group, listed in ascending order. The Red Beds are shales which vary in color from red to green, maroon, grey, grey-black, and reddish purples. They serve as marker horizons for coring the potash. The Second Red Bed averages 14 ft in thickness, the First Red Bed 35 ft. The Dawson Bay Formation, which everywhere overlies the First Red Bed and the Prairie Evaporite Formation in the area under discussion, is a reef type of carbonate, in some places limestone, in others limestone and dolomite, with vugular to pinpoint porosity averaging 130 ft in thickness. In some parts of the area, it has a salt section near the top of the formation, usually with interbedded shales and limestones. In other parts of the area, it is waterbearing and the salt is absent. Detailed mapping has indicated that the areas in which the Dawson Bay is water-bearing are areas which have been disturbed by faulting. Where the Dawson Bay is salt-bearing, the porosity has been plugged by salt. The total thickness of the salt varies from between 600 to 700 ft in the center of the basin to zero at the northern edge of the basin (Fig. 2).* The salt-free area in the center of the Province is believed to have resulted from removal of salt by solution. Evidence from several wells suggests that salt removal has been a continuing process from the time of deposition to the present day. One well drilled between the Quill Lakes for potash information encountered

Jan 1, 1961

Bailey, Lewis Newton, Master Engineer, Senior Grade, 4th Regiment, U. S. Engineers, Headquarters Company, died of pneumonia at Camp Merritt, N. J., on April 30, 1918. Baird, Louis, Lieut., Royal Field Artillery, British Army, died on the battlefield in 1915. Ballamy, John H., Capt., 103c1 Engineers, killed in action near Fismes, Aug. 9, 1918. Bowles, Martin F., 2d Lieut., Co. B, 355th Infantry, killed in action, Sept. 3, 1918. Burt, Andrew, died in active service, 1916. Cobeldick, William Morley, Royal Engineers, died from gas poisoning on Oct. 7, 1915. Dougall, Ralph,. 4th University Co., Princess Patricia Regiment, killed in action early in the war. Evans, Alfred Winter, Lieut.-Col., New Zealand Rifle Brigade, D. S. 0., D. C. M., killed in action on Oct. 12, 1917. Gordy, Sheppard B., died in service, Oct. 9, 1918. Gorman, Thomas C., Lieut., Canadian Engineers, killed in France, Mar. 18, 1918. Hague, William, 1st Lieut., Engineer Officers' Reserve Corps, died in active service, Jan. 1, 1918.

Jan 1, 1919

By H. E. Stauss, J. Hino

INTEREST in silicon has arisen again in the past decade as a result of improvements in crystal rectifiers.' Although the preparation of silicon was first reported by Berzelius in 1880, the early product was of relatively low purity, and only the need for rectifiers in World War II led to the production of a 99.9+ pct pure powder. This material in crystalline form was consolidated into massive silicon for use, and the method developed was to melt it with selected added constituents as "doping" agents. Melting techniques, therefore, are of great importance. There are two basic problems in producing silicon ingots free of doping additions; one is the prevention of spitting and the other is prevention of cracking of the ingot during freezing. The most satisfactory arrangement yet developed for producing massive silicon is to melt and freeze in a cylindrical quartz crucible surrounded by a concentric heating element and concentric radiation shields or insulation. For example, use can be made of a tubular heater with a high frequency generator as the source of power and reflecting shields of alundum cylinders. The spitting of silicon is related to gas evolution, and the gas comes from two primary causes—adsorbed gas and the reaction products of silicon and the crucible. Gas is also released from bubbles contained in the quartz crucible walls. Improved removal of adsorbed gas can be achieved by means of controlled melting and freezing. The seriousness of the problem in vacuo is reduced with an electrically operated mechanical movement of the high frequency power coil. The upper portion of the powder charge is melted first and the high frequency coil lowered until the powder is completely molten. During cooling the high frequency coil is raised slowly. These means also reduce the final nonviolent extrusion of large beads of metal through the ingot top during freezing. Better control of spitting and bead extrusion is obtained when melting is done under helium at. atmospheric pressure instead of in vacuo. The problem of reaction between silicon charge and crucible in practice is confined to the reaction between silicon and quartz. This2 apparently is: Si + SiO2 + 2SiO The part that this reaction plays in spitting has not been isolated for separate study. SiO is a volatile vapor at the melting point; of silicon and is released freely during melting in vacuo, but hardly at all in helium at atmospheric pressure. The cracking of ingots is a major difficulty in melting silicon, and its prevention requires special melting techniques or the addition of "toughening" agents such as aluminum or beryllium.' The cracking of the ingots has been explained as being the result of the expansion that occurs upon freezing; although direct observation of freezing ingots reveals visible cracks on the surface only after a red heat has been reached, suggesting that cracking is the result of differential contraction of silicon and quartz. Silicon wets quartz, and the ingot adheres tightly to the crucible. Therefore as ingot and crucible cool, the two either have to pull apart, or at least one must crack. Surprisingly, in spite of the relative thinness of the quartz and the thickness of the ingot, the ingot and the crucible both crack. Microscopic and X-ray4 studies fail to show any plastic flow other than twinning in the ingots. Slow cooling fails to prevent cracking. Another possible solution to cracking is to weaken the crucible. Use of thin-walled crucibles finally led to success with fused quartz crucibles with a wall thickness of 0.25 to 0.50 mm. With such thin-walled fused quartz crucibles consistently uniform success is secured in producing sound ingots 30 mm in diam from the purest available grade of silicon (99.9+) without the use of any type of addition. Melts are made in the size range of 50 to 100 g. Omission of a deliberately added doping agent is not sufficient to insure pure ingots. The reaction of silicon with crucibles and the resultant solution of impurities in the silicon is well-established." In this laboratory, the presence of Al, Be, and Zr has been found spectroscopically in ingots melted in contact with alumina, beryllia, and zircon. The best crucible materials reported in the literature are MgO and SiO2. Use of MgO in this laboratory has resulted in a heavy deposit of magnesium on the furnace walls, showing that a reduction of the magnesia occurred and the resulting magnesium removed from the melt by volatilization. In the case of quartz, the silica is reduced and SiO liberated to deposit on the equipment walls. There probably is real danger that oxygen is dissolved in the ingot when either magnesia or silica is used as the crucible material. Preliminary analyses by Dean Walter in his vacuum unit in this laboratory6 indicate the presence of oxygen in undoped silicon melted in quartz.

Jan 1, 1953

By W. G. SWART

THE best estimate on reserves of iron ore in the Lake Superior district is that made, in 1920, by Mr. R. C. Allen, amounting to 2,947,225,000 tons of assured and probable ore. This includes direct- shipping or so-called merchantable ores, and those capable of beneficiation by demonstrated processes. De- ducting from this the 287,000,000 tons shipped since 1920, leaves a present reserve of approximately 2,500,- 000,000 tons, or; about 50 years' supply. The assured ore in this estimate is given as 1,560,500,000 tons, which checks Mr. Lake's estimate of 1,528,948,000 tons, or about 30 years' supply. This is not a long time in the life of the steel industry, and it can be readily appreciated that the matter is important enough to war- rant the attention it is beginning to receive. The first question that engages our attention is, What is merchantable ore? In 1902 the average of all Mesabi shipments was 56.07 per cent iron and 4.35 per cent silica. Twenty-five years later it had dropped to 51.99 per cent iron, with silica up to 7.92 per cent. It has remained around these figures for' ten or twelve years and, except for a probable rise in silica, can stay there for an indefinite period. Most of these figures I am giving cover the Mesabi Range. Including the other ranges does not change the figures greatly, and the Mesabi Range commands the situation, since it produces about 65 per cent of the total annual tonnage and, according to Mr. Allen, contains 81 per cent of the assured reserves, 50 per cent of the probable reserves, and 66 per cent of both the assured and the probable reserves.

Jan 1, 1926

By M. F. Goudge, R. V. Tomkins

Sodium sulfate is an important chemical raw material that is being used in ever increasing quantities in modem industry. It comes on the market mainly in three forms: (1) Salt cake (Na2SO4), a relatively crude form of the anhydrous salt containing up to 3 pct impurities, and comprising about three-quarters of the North American production; (2) anhydrous sodium sulfate (Na2SO4), a refined form containing less than 0.3 pct impurities; (3) Glauber's salt, the decahydrate (Na2SO4.10H2O) containing 55.9 pct water of crystallization. Competing with salt cake from natural sources is byproduct salt cake from a number of industrial operations. For instance there is Mannheim cake resulting from the manufacture of hydrochloric acid by the reaction of salt (NaCl) and sulfuric acid in Mannheim furnaces; rayon cake, a high-quality product, resulting from the process of making rayon by the viscose process; chrome cake from the processing of sodium chromate to dichromate; phenol cake from the manufacture of phenol; also byproduct sodium sulfate resulting from the conversion of lithium sulfate to lithium carbonate; from the processing of sodium tetraborate to boric acid; from converting sodium formate to formic acid; and in the manufacture of cellophane. Sodium sulfate is also obtained as a byproduct in the manufacture of isosebasic acid. In addition strong competition has resulted from imports of byproduct salt cake from the chemical industries of a number of highly industrialized European countries. However in recent years due to technological changes the output of byproduct salt cake is rapidly diminishing and the natural deposits are becoming the most important source of sodium sulfate used in North America. For instance, the production of hydrochloric acid in Mannheim plants has become obsolete and thus the greatest single source of byproduct salt cake will disappear. Also viscose rayon is meeting strong competition from nylon and other synthetic fibers and production of byproduct salt cake from this source may do little more than remain at the present level. These factors together with increasing demand for sodium sulfate point to increased production from natural sources. In 1958, 36 pct of the total United States production was derived from natural sources and in addition 97,000 short tons was imported so that over 40 pct of the total consumption was supplied by natural sources whereas in 1953 the proportion was only 24 pct. The rapid growth in production is shown in Table 1. Principal Sodium Sulfate Minerals There are many minerals in which sodium sulfate is a constituent but those of commercial importance at the present time, and consisting wholly of sodium sulfate in either the hydrous or anhydrous states, are mirabilite and thenardite. Minerals of potential importance but consisting in part of compounds other than sodium sulfate are glauberite in which sodium sulfate is combined with calcium sulfate, and blödite in which sodium sulfate is combined with magnesium sulfate. Mirabilite (Na2SO4.10H2O) the decahydrate, consists of 24.8 pct SO3, 19.3 pct Na2O, and 55.9 pct H20. It is a colorless to opaque, soft, water-soluble mineral with a slightly bitter taste. It has a hardness of less than 2 and a specific gravity of 1.48. It forms long needle-

Jan 1, 1960