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By Harry V. Welch

Early in the development of the art of metallurgy, it was noted that a distinct difference existed in the character, collection possibility and health hazard of the "smoke" from lead furnaces and those from copper plants. Zinc-plant fumes, although not so detrimental to health, were closely allied in nature to those of the lead works. In Cottrell plants, there are sufficiently distinct differences in operation and amount of construction between those for lead and copper to justify their consideration under separate headings; therefore, while the application of the process at copper-reduction works was covered by the writer some two years ago in the Transactions1,† this discussion will confine itself more distinctly to "fume" collection. General information on the process has been presented in numerous articles and by many authors: Cottre112, Schmidt3, Bradley4, Anderson6, Labbe6, Shiga7, Rathbun8. "Fume" may be defined as material, metal or nonmetal, elemental or compound, evolved as a vapor from a furnacing or chemical reaction and condensing, chilling or reacting within the gas stream to yield a solid form, and in this definition liquid particles are solids in a sense as distinguished from gases or vapors. Such condensed particles are of minute form, on the order of "smoke," and, for example, on the order of a few hundredths of 1 micron (1 micron = 1/25,000 in.) to perhaps 3 microns, with agglomerates, in relatively small proportions of many particles. Metallurgically typical fume products are lead compounds, oxides, carbonates and sulphates; elemental zinc, more commonly encountered as a fume particle of zinc metal with a surrounding "skin" of zinc oxide; arsenic, both metal and oxide and some of its more complex salts such as added sulphates as found in flue dusts; antimony, more particularly its oxide forms; and elemental sulphur, sometimes a troublesome product, in Dwight-Lloyd sintering-plant fumes. These products, particularly the elemental or lower oxide forms, have relatively appreciable vapor pressures at the existing operating temperatures as reported by Welch and Duschak9, Ingold10, Johnstonll, Millar12,13.

Jan 1, 1937

By E. V. Daveler, Frank L. Antisell

CERTAIN physical and chemical properties of copper are so intimately related that a change in variation of the physical properties indicates a certain chemical change. The standard specifications of copper of the American Society for Testing Materials are based upon physical characteristics with one exception, namely, the copper contents. Certain phenomena of the surface indicate the adaptability of the metal for forging or rolling. The writer believes that it is much simpler to produce shapes that are metallurgically correct than those that are mechanically satisfactory. The appearance of the surface of the copper when cooled is considered as to its "pitch," or the general contour of the surface, and the "set," or the decail appearance of the surface of the shape. The set of the copper is, in a very large measure, directly related to the pitch; and so intimately are these characteristics connected that they are often used as synonymous terms by the refiner when he is speaking of well-refined copper. Oxygen is often spoken of as a medicine for copper, it being used to regulate the pitch.

Jan 1, 1920

By H. J. Morel-Seytoux

Methods of predicting the influence of pattern geometry and mobility ratio on water flooding recovery predictions are discussed. Two methods of calculation are used separately or concurrently. The analytical method yields exact solutions in a convenient form for a unit mobility ratio piston-like displacement. A few typical pressure distributions, sweep efficiencies and oil recoveries are presented for various patterns. For non-unit mobility ratio, one may resort to a numerical method, such as that of Sheldon and Douherty. 1,2 Because the domains of applicability of the analytical and numerical techniques overlap, the exact solutions provide estimates of the errors in the numerical procedures. The advantages of the analytical and numerical methods can be combined. To develop a numerical technique as independent of geometry as possible, the physical space is transformed into a standard rectangle. The entire effect of geometry is rendered through one term, the "scale-factor", derived from mapping relations. The scale factor can be calcu-lated from the exact unit-mobility ratio solution for the particular pattern of interest. By this means recovery performances for arbitrary mobility ratio con be obtained for many patterns. A sample of tesults obtained in this manner is presented. INTRODUCTION Pattern geometry and mobility ratio are two major factors in making a waterflood recovery prediction. Because assisted recovery has become increasingly important to the oil industry, pattern configuration and mobility ratio also assume a greater significance in the assessment of the economic value of recovery projects. The influence of pattern geometry and mobility ratio in shaping a recovery curve and on the other quantities of interest to the reservoir engineer is the main subject of this paper. Much effort has already been spent on estimating quantitatively the influence of either pattern or mobility ratio or both on oil recovery. The literature reports many investigations of this nature. 3-9 However, many results or methods of recovery prediction presented in the literature cannot be considered fully satisfactory. Even for unit mobility ratio and piston-like displacement, where analytical solutions are available, the literature shows discrepancies. For non-unit mobility ratio, the divergence in the results is extreme. For infinite mobility ratio in a repeated five-spot, depending on the investigator, the sweep efficiency ranges from 0 per cent to 60 per cent. With respect to the influence of pattern on recovery, only the repeated five-spot has received much attention. Other confined patterns and pilot configurations have received very little attention. Two calculation methods are presented in this paper, either separately or concurrently: the analytical method of potential theory and the numerical method of finite-difference approximation. The analytical method is more restricted in scope than the finite-difference method, but it has the definite advantage of providing exact solutions within its range of applicability. If a unit-mobility ratio piston-like displacement is assumed, the analytical approach is possible. A few typical results are reported in this paper; the detailed description of the general method and of a great variety of results will be the subject of other articles. Fornon-unity mobility ratio, we must resort to a numerical scheme. The numerical technique is that which was described by Sheldon and Dougherty.l,2 It is not limited to piston-like displacement. However, mainly single interface results will be presented here. Because the respective domains of applicability of the analytical and the numerical method overlap, useful comparisons of exact and numerical solutions can be made for a variety of patterns. The advantages of the analytical and numerical approaches can be combined. The reason for the success of this analytical-numerical approach can be summarized in the following two points: 1. The numerical solution for arbitrary mobility ratio can be programmed most efficiently when the physical space in which the displacement actually takes place is transformed into a standard shape; and 2. This can be done with remarkable simplicity whenever an analytical expression for the pressure

Jan 1, 1966

By J. K. Brooke, F. A. Renninger

During 1966, crushed stone production in the United States totaled just over 811 million tons valued at almost $1.2 billion. This represented in- creases of 4 % in tonnage and 5 % in value over that for 1965. Excluding the crushed stone used for agricultural and certain industrial purposes (cement, lime and flux), crushed stone mineral aggregate production totaled 616.3 million tons valued at almost $910 million, also up roughly 4% in tonnage and 5% in value over the 1965 figures. Limestone was by far the most widely used rock variety, followed by basalt, granite and sandstone in that order. Concrete aggregate and roadstone continued as the main uses for stone, accounting for 63% of all tonnage produced in 1966 and 60% of total stone value. Sand and gravel production in 1966 increased 3% over that for 1965. Total 1966 output was just in excess of 934 million tons valued at almost $985 million as compared with 908 million tons at $957 million for the previous year. Excluding the higher valued industrial sands, 903.2 million tons of sand and gravel valued at $891.6 million were used directly as mineral aggregates, representing a 2.9% increase in tonnage and a 2.4% increase in value over 1965.

Jan 2, 1968

By George Espey, George Sachs, G. B. Kasik

IT has been reported frequently that the hardness and strength vary over the cross section of cold-worked, particularly cold-drawn, material. Brass rod and wire usually have been found to possess a maximum strength and hardness near the surface.1,2 According to Sachs,' the center fiber has about the same strength as a wire stretched by the same amount in a tensile-test machine, the strength increasing toward the surface (Fig. I). These differences are particularly large for wire given a small reduction on drawing through a die with a wide opening. However, with increasing reduction and hardness, a tendency to form a thin soft surface skin becomes apparent. On the contrary, copper wire has usually been found to possess a soft surface skin3-5 and it has been reported by Harris3 that during the cold-drawing of hot-rolled wire the surface layer becomes increasingly softer than the core, while the layer of maximum strength moves toward the core, it being found near the surface at first. The increase of strength and hardness from the core to the skin is readily explained by the observation that, in addition to the stretching, the layers of a rod or wire are sheared more the closer they are to the surface.1,6-8 However, the presence of a soft surface layer can be attributed only to an annealing effect. The source of such a softening might be the extremely high temperature that originates from the friction between

Jan 1, 1942

By G. B. Kasik, George Sachs, George Espey

IT has been reported frequently that the hardness and strength vary over the cross section of cold-worked, particularly cold-drawn, material. Brass rod and wire usually have been found to possess a maximum strength and hardness near the surface.1,2 According to Sachs,' the center fiber has about the same strength as a wire stretched by the same amount in a tensile-test machine, the strength increasing toward the surface (Fig. I). These differences are particularly large for wire given a small reduction on drawing through a die with a wide opening. However, with increasing reduction and hardness, a tendency to form a thin soft surface skin becomes apparent. On the contrary, copper wire has usually been found to possess a soft surface skin3-5 and it has been reported by Harris3 that during the cold-drawing of hot-rolled wire the surface layer becomes increasingly softer than the core, while the layer of maximum strength moves toward the core, it being found near the surface at first. The increase of strength and hardness from the core to the skin is readily explained by the observation that, in addition to the stretching, the layers of a rod or wire are sheared more the closer they are to the surface.1,6-8 However, the presence of a soft surface layer can be attributed only to an annealing effect. The source of such a softening might be the extremely high temperature that originates from the friction between

Jan 1, 1942

Trans. Pamphlet Volume Number Title Author Meeting and Page* 1033 Relation of Air Presaure to Drilling H. W. Seamon New York 66, 743. 766 Speeds of Hammer Drills . Feb. 1921 1034 Time Factor in Depletion of Mines J. W. Roberts New York 66, 711 Feb., 1921 1035 Calculation of Ore Tonnage and Grade J. E. Harding New York 66, 117, 122 from Drill-hole Samples Feb., 1921 1038 Diacuasion of Papers Presented in 1920 1041 Run-off and Mine Drainage H. N. Eavenson New York 66. 624. 630 Feb.. 1921 1043 The Health of the Underground Worker A. J. Lanza New York Feb, 1921 1045 Dust-ventilation Studies in Metal D. Harrington New York 66, 272, 288 Mines Feb., 1921 1046 Discussion of Papers Presented at New York Meeting, 1921 1072 Breakage and Heat Treatment of Rock- B. F. Tillson New York 66. 758 drill Steel Feb., 1921 1073 Discussion of Papers Presented at New York Meeting, 1921 1076-M Analysis of Some Drill-ateel Teats F. B. Foley New York 66,789 Feb.. 1921 1077-M Application of Magnetic Analysis to C. W. Burrows New York 66, -796 Rock Drills Feb., 1921 1078-M Heat Treatment of Rock-drill Steel G. H. Gilman New York 66.779 Feb., 1921 1080 What is the Ideal Drill Steel? F. H. kingdon New York 66, 807 Feb.. 1921 1081 Rock Drill-Steels, etc. W. T. Ober New York 66,814 Feb.. 1921 1082-C Underground Mine Development, Its J. B. Dilworth Wilkes-Barre 66,715, 761 Definition and Valuation Sent.. 1921 1081 Drill Steel from Hollow Ingots P. A. E. Armstrong New York 66,809 Feb., 1921 1068 Authors' Replies to Recent Discussion 1092 Heat Treatment of Rock Drill Steel A.E.Perkins New York 66,811 Feb., 1921 1096-M Octagonal Ventilation Shaft of Davis- J. L. Bruce Wilkes-Barre 66. 252, 608 Daly Copper Co. Sept., 1921 1100-C Determination of Electrical Equip- G. Bright Wilkes-Barre 66,580,606 ment for a Mine Hoist Sept., 1921

Jan 1, 1927

By AIME AIME

FREE competition, long the controlling ideal of domestic trade within the United States, has had the fundamental geographical advantage of functioning in the world's largest area of unrestricted commerce. Goods moved back and forth across state lines, unimpeded by customs, and industrial operations have developed rapidly to meet the expanding needs of a pioneer country richly endowed with natural resources. Fifty years ago, antitrust laws were adopted to protect the competitive private enterprise principle. It became illegal for one person to combine with another to restrain trade or commerce among the several states or with foreign nations. The original legislative measures defining this philosophy were the Sherman Act of 1890 and the Clay- ton Act passed in 1914. The development of Europe and other parts of the world was influenced by different conditions which led to a different theory of trade. Here were many small nations, with limited natural resources and a thin market, and they attempted to protect their national economy by tariff walls. International business arrangements for the purpose of diminishing the ups and downs of the more competitive system --crux of the modern cartel operations-seemed a logical device to stabilize production and guard the interests of both workers and consumers. European governments as well as European industrial interests became convinced that if com- petition could be held in bounds the danger of business depressions and un- employment could be reduced.

Jan 1, 1944

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper' the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called ('deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,' it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2'3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,' indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By T. R. Graham, R. G. Feustel, J. R. Long, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By J. R. Long, T. R. Graham, R. G. Feustel, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By M. B. Bever, A. K. Jena

Equations for the heat effects of additions of mixtures of multicomponent phases to a solution have been derived in terms of the enthalpy interaction coefficients. By these equations and the measured composition dependence of the heat effects on addition of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions, values of the enthalpy in-teraction coefficients in tin-rich solutions at 541°K have been obtained. Analysis of these results in terms of the regular solution theory and the quasichemical theory suggests that near the melting point of the solvent association in the solution becomes important. SEVERAL recent papers have discussed the nature of dilute solutions on the basis of measured enthalpy interaction coefficients. l-3 These coefficients contribute to the understanding of the constitution of solutions and can be used for the evaluation of thermo-dynamic data of multicomponent systems. Their experimental determination, however, is laborious. This communication reports values of the enthalpy interaction coefficients of silver, cadmium, and gold in liquid tin-rich solutions obtained from the measured heat effects of additions of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions. These measurements were made in the course of the determination of the heats of formation of Ag-Cd solid solutions reported in a concurrent publication.4 THE HEAT EFFECT OF AN ADDITION TO A SOLVENT This analysis is concerned with the addition of a mixture of multicomponent phases from the temperature To to a solvent of known composition at temperature T. If Nmixture << Nsolvent, where N designates the gram-atoms involved, the heat effect per g-atom of mixture added can be expressed as (HT - HT )i = difference in heat contents of component element i in the mixture at T and To Q = heat effect on solution of the mixture at temperature T Also1 Q = S Xi [2] where ?Hi ,T,x = relative partial enthalpy per g-atom of i in solution at temperature T and composition of the solution x x = average of the atom fractions of the added material in solution before and after the addition The relative partial enthalpy ?Hi per g-atom of an element i in a dilute solution composed of a solvent 1 and the solutes j = 2, ... m is related to the interaction coefficients by the following equation5 ?Hi - ?Hi-?Hi,x1-1 + S n1ixj+ . . . +S...S...S nrixn2... Xnji...Xnmm+... [3] vhere Xj = atom fraction of solute j in the solution nri = the rth order enthalpy interaction coefficients, which can also be represented by the more general designation5 L(i)n2,n3...nm and nj may have any positive integral value or zero. For identification of various rth order interaction coefficients, nri is written as nn2i2,...nij,...nmm. Eqs. [1], [2], and [3] combine to give the following general equation for the heat effect on addition of a small quantity of a mixture to a large quantity of a dilute solution n = _?ga ?Ha,To + ? Xi(HT - HT o)i a. i + ?xi?Hi,X,i?1 + ??xnjixj + . . . + ???. . .?. . .?xinrix2n2. . . xnji. . . xnmm+ . . . [4] The first term on the right-hand side of this equation is the heat of decomposition at the addition temperature of the phases present in the mixture, the second term is the heat required to raise the temperature of

Jan 1, 1970

By D. N. Seidrnan

In the present note we present thermal-analysis data for the liquidus curve from 0 to 76 at. pct Se and for the selenium-rich monotectic reaction in the Pb-Se system. We have previously reported that no expey-imental eviderzce was found for a lead-rich monotectic reaction, at -860°C with a monotectic composition of -20.5 at. pct Se, as found by Nozato and Igaki.&apos; Our additional data substantiated this earlier finding and extended the composition range studied. The alloys were prepared from semiconductor -grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999+ wt pct pure as determined by the supplier. The impurities for lead were Fe (1 ppm) and Cu & ppm) while for selenium the impurities were Cu (< 1 ppm), As (< 1 ppm), Te (1 ppm), and C1 (<1 ppm). The general procedures used for thermal analysis were those specified by the National Bureau of Standards. A Pt/Pt-10 pct Rh thermocouple calibrated against the freezing points of zinc and copper purchased from the National Bureau of Standards and antimony (99.985 pct pure) purchased from A. D. Mackay, New York, was used for all the thermal analysis. The thermocouple electromotive force was measured with a Rubicon Type B potentiometer used in conjunction with a galvanometer with a sensitivity of 0.5 pV (mm) -&apos;. The absolute accuracy of this thermal-analysis system was *0.5"C. One-hundred-gram alloys of the desired composition were sealed in quartz crucibles, with a central thermocouple well, at a pressure of less than 10"1 Torr. The alloys were initially heated well above the liquidus curve and shaken vigorously to insure homogeneity. Cooling curves were then taken by the direct method at cooling rates ranging from -0.5" to 1.5"C (min)-&apos;. The phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis is shown in Fig. l.* An extrapolation of the selenium-rich portion of the liquidus curve to the monotectic reaction isotherm (678.3"C) gave a value of 76.1 at. pct Se for the monotectic composition. A tabulation of all the thermal-analysis data is given in Table I. As we previously reported no experimental evidence was found Fig. l—The partial Pb-Se phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis. For the sake of clarity the points for the 49.00 and 49.16 at. pct Se alloys were not drawn on this phase diagram, see Table I. for the lead-rich monotectic reaction found by Nozato and Igaki.&apos; This result was further substantiated by the fact that none of twelve lead-rich alloys, see Table I, examined for this monotectic reaction exhibited a thermal arrest in the temperature range (849" to 863°C) cited by Nozato and Igaki for the lead-rich monotectic reaction. Hence, our results tend to support the earlier qualitative work of ~elabon&apos; and Friedrich and ~eroux" in the 0 to 50 at. pct portion of the phase diagram, though the selenium-rich monotectic composition and reaction isotherm temperature were in agreement with the approximate values (75 at. pct Se and 672" to 680°C) given by Nozato and ~~aki. &apos;

Jan 1, 1967

By L. W. Sink, B. H. Kear, S. M. Copley, M. F. Hornbecker

IT is well known that under appropriate conditions of chill casting, many metals and alloys develop a columnar grain structure having a high degree of preferred orientation.&apos; In cubic materials, this principle has been employed to produce shaped castings with a unidirectional cube oriented columnar grain structure as well as shaped single crystals with a cube axis parallel to the growth ais.&apos; "he purpose of this note is to describe how this same principle can be enlployed to produce wires, rods, or more complex crystal Shapes with a variety of conlpositions in cube or random orientations by a single casting operation. The procedure for directional solidification of in Fig. 2. Examination under crossed polarizers indicated that the striations were a second phase (presumably the B19 phase) which frequently forms initially at primary grain boundaries and then grows toward the interior as thin ribbons. X-ray studies on filings of this alloy reannealed at 1300°C for 15 min indicated a strong pattern of the fcc phase together with a substantial pattern of the B19 phase. The un-annealed filings, however, showed only the pattern of a cold-worked, fcc structure. In these two-phase alloys it appears, therefore, that the B19 phase is transformed into a disordered fcc structure by cold-working. The mechanical properties of these alloys would be of some interest since a fcc structure might be expected to possess greater ductility than the or-thorhombic B19 structure from which it forms. The author wishes to thank Mr. Harvey Yakowitz and Mr. Richard Manuszewski for obtaining the photomicrograph in Fig. 2. This research was partially supported by Research Grant DE-02455 from the National Institute of Dental Research. columnar grained ingots involves pouring a melt into a preheated mold having a water-cooled copper chill at its base? and controlling the temperature gradient in the mold so as to maintain columnar grain growth from end to end of the ingot.4 This is illustrated schematically in Fig. l(a). It should be noted that the longitudinal temperature gradient promoting unidirectional columnar grain growth is maintained by heat loss primarily through the solidifying ingot to the chill, so that both the temperature gradient and the growth rate diminish with increasing distance from the chill. As the distance from the chill increases? the columnar structure coarsens, and the perfection in preferred orientation tends to increase progressively. Using this same procedure of gradient solidification, Fig. l(b) shows a simple scheme for producing a batch of crystals having the same cube orientation rather than an assemblage of columnar grains. Wires and rods are produced by cementing ceramic tubes to the wall of the mold. The steep temperature gradient produced in the central chamber is controlled by the mold heater to produce favorable conditions for crystal growth. Clearly the success of the operation lies in the selection of individual growing columnar grains by some kind of orifice at the base of each channel in the mold. Using simple constrictions, experience with nickel-base alloys has shown that 4 -in.-diam holes at a distance of -1 in. from the chill yield crystals within 7 deg of (100); closer control of orientation is possible by placing the crystal selector farther away from the chill.

Jan 1, 1970

By E. D. Glass, R. C. Hessing

The volume of gas in storage reservoirs may be compuled from estimates of hydrocarbon pore volume and gas density. However, both are dificult 10 estimate accurrately. Further, no adequate method has been presented for estimating reservoir performance during operation for Volumetric gas-storage reservoirs. Normally, gas-storage reservoirs exhibit small pressure gradients in the area conr(zilliitg the storage wells, even under conditions of maximum injection or withdrawal. A zone of low permeability usally surrounds, and is in communication with, tile permeable zone which causes the storage reservoir to exhibit a definite pressure lag, as evidenced by lack of pressure stabilization after extended periods of shut-in. An analysis is presented for determining pore volume and gas in place, and for predicting future reservoir behavior of such reservoirs. The mathematical development is presented and a solution is shown for an operating storage reservoir. INTRODUCTION Depleted gas reservoirs arc often used for gas storage. The reservoir usually contains a permeable area in which numerous storage wells arc located. The permeable zone permits high deliverability and injectivity with relatively small pressure loss. However, pressure equilibrium may not be attained even after long periods of shut-in because of the fact that the permeable zone is in communication with an adjacent tight section. Most of these gas-storage reservoirs are sand lenses, such as ancient beaches or offshore bars. The areal geometry of these reservoirs is normally such that flow in the tight zone will be approximately linear, and the solutions presented here should apply. DISCUSSION For purposes of this paper, a gas-storage reservoir is considered to consist of a volume of permeable rock in communication with tight rock, all of which is surrounded by an impermeable barrier. Pressure gradients across the permeable zone are small due to low flow resistance and well density. Hence, the permeable zone is considered to be at a uniform pressure which is only a function of time as gas is injected or withdrawn. The tight zone is considered to be linear with uniform permeability and porosity, and the pressure in the tight zone is a function of both position and time. l&apos;wo solutions for flow in this system are used to define the reservoir and determine its properties. The first solution is for an infinite linear tight zone in communication with the permeable zone. The expression for constant gas-withdrawal rate is Eqs. I and 2 ore superposed to account for varying rates of production or injection and are used to fit gas-storage field reservoir history. The solution for the infinite case, Eq. 1, is first applied to field data for early times following a shut-in period. Constants BDa and c are ohtained by a least-squares fit of pressure and rate data. After the pressure wave from gas injection or withdrawal reaches the external boundary of the tight zone, the infinite solution will no longer apply and pressure behavior should be more nearly represented by Eq. 2 for a gas reservoir in communication with a finite linear tight zone. The values of the constants found from curve-fitting Eq. 1 to the early time data may then be used in Eq. 2 that only the coefficient- L containing the unknown

By J. Kucera, J. Vreštál

DIFFERENT authors1 &apos; have been engaged in meas-uring the vapor pressure of pure cobalt. The results of their measurements satisfy the expected temperature dependence of vapor pressure and are in mutual agreement, with the exception of the results by De Dyk Man and ~esmejanov.~ The latter authors, by using the effusion method, have achieved considerably higher values than other workers. By using the isotope exchange method they obtained much lower values than other authors. The determination of thermodynamic functions of the binary Ni-Co system was carried out, as far as we know, only by De Dyk Man and Nesmejanov.4 This determination was based on extremely low values of vapor pressure over pure cobalt obtained by the isotope exchange method. Therefore we considered it useful to repeat these measurements. Furthermore, the reliable values of thermodynamic functions should complement the migration characteristics, the inner magnetic field data obtained by Miissbauer effect measurements, specific heat data, and the K effect and positron annihilation characteristics that have been achieved for the Ni-Co system in the Institute of Metallurgy of the Czechoslovak Academy of Sciences in Brno.5-9 The measurements in this paper were performed by the isotope exchange method. In this method, as has been shown by analysis,10-&apos;3 the vaporization rate, w, can be calculated from the relation w = k/1oSw [1] i0Sw) [1] where L, is the activity per unit mass of the source, S is the area of evaporation, k is the tangent at the point t = 0 to the curve giving the radioactivity de-pendence of the target vs annealing time, t, and wis the probability for the tracer atom condensation on the target surface. The value for cc. can be obtained from the equation w = a + 2P(l-a) [2] where P is Clausing&apos;s coefficient and a is the condensation coefficient. In the present work the cylinder shaped containers for annealing the samples were used, characterized by the ratio 1:d = 1.06. Here 1 is the length and d the diameter of the container. For this ratio P = 0.514 and w =0.5, and w is independent of the condensation coefficient. The vaporization rate is related to the vapor pressure p by the relation where R is the gas constant, T is the absolute temperature, and M is the molecular weight of the component investigated. Measurements of the vapor pressure of the i component over the pure metal, p!, and the alloy, pi, at the given temperature and composition enable one to calculate the thermodynamic activity of this component from the equation ai=pi/pi [4] is and the activity coefficient ri=ai/xi [5] xi where xi is the molar fraction of the investigated alloy component. EXPERIMENTAL Evaporization rate measurements were carried out with pure cobalt and eight different Ni-Co alloys, which were kindly delivered by the Centre National de Recherches Me&apos;tallurgiques Liege, Belgium. The composition of the alloys is given in Table I. The cobalt used in these alloys contained the following impurities: 0.016 wt pct Fe, 0.014 wt pct Cu, 0.01 wt pct Mn. Other elements were present in much lower concentrations. From the melts, samples in the form of small cylinders of 12 mm in diam were ma-chined. The thickness of the targets and sources was 2.5 and 1.2 mm, respectively. The lower thickness of the sources was chosen to make their over-all ac-tivity as low as possible. Sources were activated in

Jan 1, 1970

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring&apos;s predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,&apos; who applied Eyring&apos;sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann&apos;s constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers&apos; data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By Fred R. Ingram

FOR the purpose of this discussion, let us consider that the Rocky Mountain region covers the area in the seven Mountain States, Idaho, Montana, Wyoming, Utah, Colorado, New Mexico, and Arizona, and before we discuss the needs of these states, let us define Industrial Hygiene. Industrial Hygiene is that branch of preventive medicine concerned with the protection of health, improvement of efficiency, and prolongation of life of the industrial worker; in short, adult health conservation. It includes in its broad meaning not only the prevention of occupational diseases, such as silicosis, lead poisoning, cadmium poisoning, and many others, but such relative problems as overcrowding, fatigue, and personal and mental hygiene; exposure to abnormal temperatures, pressures, and humidities; ventilation, heating, and lighting. It is a science which requires the combined activity of medical personnel (doctors and nurses), engineers, and chemists to evaluate the exposures and determine the means of eliminating the hazard. The engineer surveys the workplace, takes air samples at the breathing level of the workman, and analyzes the work exposure. The chemist determines in his laboratory the exact amount of toxic material collected in the sample, which represents the exposure of the workman. The doctor must diagnose the occupational disease, recognize its cause, and evaluate the disability. Together, all three must correlate the data obtained and devise efficient methods, medical or engineering or process changes, for controlling or minimizing the dangerous condition and for studying the effectiveness of these measures. The plant doctor, in addition, must aid in the readjustment of the incapacitated worker and provide facilities for prevention. Industrial hygiene, however, is of no avail without the understanding co-operation of management.

Jan 1, 1945

By Prof John E. Church

ONE of the most striking phenomena connected with the mines on the Comstock lode is the extreme heat encountered in the lower levels. This heat is not due to the burning of candles, heat of the men, and decomposition of timbers, all intensified by bad ventilation, as was the case nearer the surface. It proceeds from the rock, which maintains constantly a temperature very much higher than the average of the atmosphere in Nevada. The heat of these mines is a matter of more than usual interest, for they are the only hot ones now worked in the United States, and both in the present temperature encountered and in the increase which is to be expected as greater depths are reached, they appear to surpass any foreign mines of which we have a record. Hot mines are known also in other countries, as in the tin and copper lodes of Wales, where one of the veins worked by the United Mines is known as the hot lode. It has springs which discharge water at a temperature of 116&apos; Fahrenheit, the depth being 220 fathoms, or 1320 feet. The heat of the air in these workings is. given at 100&apos; to 113&apos; Fahrenheit. The air is bad, and the heat in the drifts seems to be traceable to defective ventilation rather than to the real necessities of the case. Air is supplied through a small pipe, and is drawn from a place where the temperature is 95&apos; Fahrenheit. Under such circumstances it is not surprising to read that in this hot mine the air is hotter than the rock, a state of things which I hare never observed in the Comstock. Other mines have been reported to the British Coal Committee as having temperatures of 106" Fahrenheit and thereabouts, but the only positive comparisons that are available at this writing are the following, all from Cornish mines : Mine. Depth Temperature. in feet. Air. Rock. Tresaveau,.....1581 86° 83° to 85° Consolidated Mines,. .. 1500 87° 86° " " . 1722 94o 93° " L .. .. 1764 94o to 96° 921/2° to 931/2°

Jan 1, 1879