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By W. R. Hibbard

Although extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110) , [111] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampton5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr in a standard mer-curous nitrate test. Edmunds12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wasserman11 reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. Preparation OF Specimens Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5, 10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. Determination of Pole Figures A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pet nitric acid to 0.0015 in. thickness and (111) pole figures were determined using copper K-alpha radiation in the manner described by Brick.' The three general types of pole figures

Jan 1, 1949

By W. R. Hibbard

Although extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110) , [111] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampton5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr in a standard mer-curous nitrate test. Edmunds12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wasserman11 reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. Preparation OF Specimens Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5, 10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. Determination of Pole Figures A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pet nitric acid to 0.0015 in. thickness and (111) pole figures were determined using copper K-alpha radiation in the manner described by Brick.' The three general types of pole figures

Jan 1, 1949

(The paper by L. H. De Wald-Tech. Pub. No. 429 was presented at the Boston meeting, September, 1931.) W. A. SCHEUCH, Chicago, Ill.-Since starting up our Hawthorne copper wire plant we have found that wire bars from certain suppliers perform quite differently from those of other suppliers. In attempting to evaluate these bars, we made cross-sections, and in making these cross-sections we found considerable variation in the crystal structure. Indications were that there was some preference in the type of crystal structure. In attempting to find the reason for that we discussed it with the various producers and-also reviewed the literature. Mr. DeWald was assigned to determine the various factors that enter into copper wire bar crystal structure, on the basis that the product was a horizontally cast wire bar of practically identical composition and of recognized good composition for the present quality product sold in the market. Mr. DeWald has asked me to say that he should have made reference to Mr. Dalzell's paper on a theory concerning gases in refined copper. D. K. CRAMPTON, Marion, Conn. (written discussion).-Mr. DeWald has set forth an interesting and thorough exposition of the factors controlling macrostructure of this material. It is particularly interesting to us as it somewhat parallels work we have done on macrostructure of round copper billets for piercing into tubes. Our findings as to the effect of the several variables on macrostructure check Mr. DeWald's. The general principles underlying the two are precisely the same. The fact that we worked with copper deoxidized with phosphorous instead of tough-pitch copper, and round billets cast on end instead of wire bars, does not influence the results. We have found that round billets cast so as to produce large radial grains have greater soundness and density than those with a fine macrostructure. Further, and more important, we have found that the billets with large radial grains show markedly different performance on piercing from those having a fine equiaxed structure. With a given temperature of billet and adjustment of piercing machine, the coarse-grained material requires appreciably lower power for piercing and goes through the operation inn appreciably less time. These two differences are of sufficient commercial importance to warrant exercise of great care in maintaining the coarse structure. It seems probable that much the same phenomenon should hold in the hot rolling of tough-pitch wire bars. We would expect that, other things being equal, the coarse-grained wire bars would roll more readily and require less power than fine-grained ones. Moreover, we believe the differences in initial structure of the wire bars should be largely eliminated in the hot rolling process and during the subsequent drawing and annealing, of wire would be entirely eradicated.

Jan 1, 1932

By Walter R. Hibbard

ALTHOUGH extensive pole figure studies have been reported by Brick1 and others2,3 showing preferred orientations in rolled and annealed 70-30 alpha brass, and by Hermann and Sachs4 in 70-30 alpha brass cups, comparatively little information has been published on textures in drawn 70-30 alpha brass tubes. Crampton5 reported a (110), [III] texture in drawn brass tubes based on selected individual X ray photograms following the method of Norton and Hiller,6 but the extent and ease of developing this texture and the annealing texture have not been reported and pole figures of these structures were not found in the literature. The present investigation was further stimulated by the possible influence of textures on the mercury stress-corrosion cracking of brass tubes. According to Snoek,7 iron-nickel alloy sheet with a strong cubic texture was more resistant to corrosion than a randomly oriented sheet. Crampon5 reported that single crystals of 70-30 alpha brass drawn into tubes did not crack after 24 hr s in a standard mercurous nitrate test. Edmunds 12 found that single crystals of 70-30 alpha brass did not crack in a standard mercurous nitrate test but did crack when subjected to ammoniacal vapor. Wassermann reported a similar failure of a single crystal of brass in ammonia. A tube with a strong texture might approach single crystal behavior and tend to resist mercury cracking if the differences in orientation between adjacent grains were sufficiently slight. PREPARATION OF SPECIMENS Crampton's5 tubes drawn 28 pct reduction in area developed a slight degree of preferred orientation while in tubes drawn 48 pct it was more marked. Based on this information, in order to obtain specimens with markedly different degrees of preferred orientation but with the same final draw, two sets of 70-30 alpha brass tubes were made following the mill schedules shown in Table I. The final draw involved a large reduction in outside diameter, and a ratio of reduction in area to reduction in outside diameter similar to that reported by Crampton,5,10 to cause mercury cracking of brass tubes. The brass contained 71.31 pct copper, 0.01 pct lead, 0.01 pct iron and zinc by difference. DETERMINATION OF POLE FIGURES A 6-in. length from each tube was rotated rapidly by an electric stirrer in 25 pct nitric acid until the gauge was reduced to 0.003-0.005 in. The tubes were carefully cut longitudinally and the walls gently flattened. They were further etched in 25 pct nitric acid to 0.0015 in. thickness and (III) pole figures were determined using copper K-alpha radiation in the manner described by Brick.1 The three general types of pole figures

Jan 1, 1947

By Donald L. Katz, Leo B. Bicher

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By Leo B. Bicher, Donald L. Katz

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By Joseph J. Yancik, Leonard L. Felts, George B. Clark

LITTLE information has been published concerning the actual or useful amount of energy obtained from explosives when they are used for blasting. To provide more data on this subject, 8-in. neet cement cubes were blasted in a steel plate box and the breakage energy evaluated by comparison with drop crusher results using Rittinger's,1,2 Kick's: and Bond's' theories. Theories by Bond and Wang," Lineau," Hatch,' Roller,' and others0-11 were not considered applicable. Those used in this investigation may be expressed mathematically as follows: Rittinger Theory E = KrS2, pet,—--------------- [1] 40 d1 d0 Kick Theory TV 1 1 E = =K, [S pct. log1/d+ 100 log d0] [2] 40 d1 L. L. FELTS, Junior Member AIME, was formerly a Graduate Assistant, University of Illinois. G. B. CLARK, Member AIME, was formerly Professor of Mining Engineering, University of Illinois, and is now Chairman, Dept. of Mining Engineering, Missouri School of Mines and Metallurgy. J. YANCIK, Junior Member AIME, is a Graduate Assistant, Missouri School of Mines and Metallurgy. This paper, TP 4213A. is revised from a thesis submitted by L. L. Felts in partial fulfillment of the M.S. degree in Mining Engineering, University of Illinois, 1954. Discussion may be sent (2 copies) to AIME before May 31, 1956. Manuscript, Dec. 27, 1954. Bond's Third Theory E = Kb [S pct. log1/d1+ 100 log d0] where E — energy used in breakage, d, = average diameters of screen fractions of broken cement particles, pct, = percent weight of diameter d;, and 2 pct, = 100 pct. The above equations were employed to determine values of Kr, Kk, Kb for particle size distributions similar to those obtained from the blasting curves. These values were in turn used as a means of approximating the specific energy of the blasted material. The efficiency of crushing by blasting was then determined by dividing this specific energy by the maximum available work of the explosive per gram of cement. Knowledge of the failure of solids under static loads is developing very rapidly. Their failure under impact loads has been investigated and reported in the literature only to a limited extent. Theories of failure' hnder static loading include 1) the maximum stress theory, 2) the maximum strain theory, 3) the theory of constant elastic strain, 4) theory of maximum shearing stress, and 5) Mohr's theory of strength. All of these have elements of usefulness in establishing an applicable theory for blasting. For highly strained and compressed material such as that surrounding a detonating charge of high explosive, the Mohr theory and its implications appear to be the

Jan 1, 1957

By C. E. Sims

THE carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example,, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath. The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner without reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature. For the carbon-oxygen reaction C + 0 [=] CO this is expressed simply as [ ] where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1947

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By J. P. Hirth, G. M. Pound

The flux of evaporation J from {loo) , {111), and (110) planes of silver single crystals and from poly crystalline specimens was measured at 744°C under a high vacuum using a time average weight loss method. The evaporation coefficient a was computed from the measured flux and vapor pressure data through the relationship J = aPe/21rmkT. The evaporation coefficients for the close packed planes and the poly crystalline specimens were found to be about 0.4 providing tentative confirmation of the theoretical limiting law for evaporation of metal crystals, a = 73(P/Pe) + % . The (110) planes faceted to form (111) planes, resulting in a greater evaporating area and larger a . The evaporation morphology of the plane surfaces and the surfaces of spherical single crystals is described in some detail. RECENTLY a detailed theoretical analysis of the mechanism and kinetics of metal crystal evaporation was made.1&apos;2 A mechanism for vaporization involving the recession of monatomic ledges across a metal surface was deduced, and evaporation rate equations were derived by considering the dynamics of these ledges. In most metals, the process of evaporation is one of dissociation of atoms from ledges, surface diffusion, and desorption. The gross vaporization rate is controlled by the surface diffusion and desorption rates. It was shown that the monatomic ledges, under the action of surface diffusion gradients, tend to assume a terminal velocity and spacing. Further, it was shown that crystal edges and grain boundaries are a ready source for monatomic ledges. In the case of evaporation of large, perfect crystals with clean, low-index surfaces, the kinetic treatment1 leads to a limiting law for crystal evaporation: where J is the gross flux of vaporization, a is the evaporation coefficient, Pe the equilibrium vapor pressure, m the atomic mass, k Boltzmann&apos;s constant, T the absolute temperature, and P the actual pressure of vapor over the crystal surface. Imperfections such as grain boundaries, pores, cracks, and macroscopic steps should have the effect of causing positive departures from this limiting law. Such an imperfection is a source for monatomic ledges, which, near their origin, are closely spaced and thus give rise to higher evaporation rates there. However, under many experimental conditions,&apos; this effect should be negligible due to the relatively low concentration of imperfections. In general, a more important cause of positive departure should be screw dislocations, and the effect of these has been considered in some detai1.2,3 Monatomic ledges emanate from points where the surface is intersected by a dislocation with a screw component normal to the surface. The dynamics of ledges arising from a screw dislocation are similar to those of ledges arising from a crystal edge. There is a perturbed region near the origin where the monatomic ledges are, under certain experimental conditions, closely spaced and the

Jan 1, 1960

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-&apos; have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

Discussion of the paper of G. K. Burgess and J. J. Crowe, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2537 to 2591. HENRY M. Howe, New York, N. Y. :-I think we can hardly rate the importance of the entry of the Bureau of Standards into our field. There is no body in the world that is better fitted to undertake this work than that Bureau, and it is work which really calls for the aid of some national organization. The skill and care with which this work has been done speaks for itself. It is very striking that within a very few months the distinguished English investigator, Professor Carpenter, of whom I spoke before, thought that he had disproved the existence of beta iron by proving that the A2 retardation which Professor Burgess has now demonstrated did not occur. Dr. Burgess&apos;s demonstration of the existence of. this retardation makes the existence of beta iron very probable, in my opinion. Osmond used to call beta iron " decipuum." You knew of its existence as you know of the existence of certain planets, only by the perturbation which it caused. Certain phenomena could not be explained, except by assuming the existence of a third allotropic form, beta iron. The evidence that you got was always evasive and susceptible of other explanations, except that which we have to-day, which it seems to me is not capable of other explanation. Professor Carpenter proceeded in the same way that Dr. Burgess has, by taking the heating and cooling curves of exceedingly pure iron, and thought that he had shown that there was no thermal change, no absorption or evolution of heat at the supposed A2 point, and hence that the A2 point did not exist. This he did by a piece of reasoning which I think seems to most of us rather surprising. That is to say, if of ten witnesses, three have seen a thing and seven have not, the evidence of the seven who have not is set aside, and that of the three who have seen stands. In Dr. Carpenter&apos;s own experiments under certain conditions he found the A2 change, the heat evolution., under certain others he did not. That is like the three witnesses who saw and the seven who did not see. You can arrange your test so that this change will not become visible or so that it is masked. But though an existent change can be masked a non-existent one cannot be shown. So that the reasoning seemed to me wholly fallacious.

Jan 12, 1913

By C. S. Matthews, H. C. Lefkovits

The performance of depletion-type reservoirs at the stage in which the gas is at such low pressure that gravity is essentially the sole driving force has been investigated both theoretically and by use of scaled models. A simple theory is developed which completely explains the scaled model experiments. It also agrees with some field data. When the range of production rates to be considered is less than 25, the theory predicts that the production rate decline curve for homogeneous reservoirs in which there is a free surface will be of the hyperbolic type with n = 2: The theory gives a physical significance to the parameter y. INTRODUCTION This investigation was undertaken to determine a method for prediction of performance of reservoirs where gravity is the sole driving agent. Depletion-type reservoirs fall into this category after the pressure has fallen to some low value. Some examples of this type are found at Healdton (&apos;Oklahoma), Oklahoma City (Oklahoma), Midway-Sunset (California), and East Coalinga (California). Generally the production rate per unit thickness is quite low in such reservoirs, with the conse- quence that this stage is sometimes called the stripper stage. However, per well production rates may be of the order of 50 B/D because of the considerable sand thickness open in some of the reservoirs. In the past, predictions of behavior of such reservoirs have been based on empirical extrapolation of the rate of production to the economic limit. Difficulties arise when new wells are drilled in the field or when production is artificially curtailed, since in such cases the decline rate of individual wells or leases changes and no clear trend can be detected. It was hoped that the present study would lead to improved methods for evaluation of such reservoirs. The study was initiated by building a scaled model for a particular field and by running a number of experiments on this model. Later a simple theory was developed which explained the laboratory results completely. The theory led, as shown below, to a hyperbolic-type decline equation which had been used previously&apos; in a completely empirical manner. THEORY The General Case The problem to be treated here is the following: We are given a homogeneous cylindrical porous reservoir with exterior radius r, wellbore radius r., and height h,, containing, from the bottom up to a height hit oil, some gas, and interstitial water (see Fig. 1 A). The portion of the reservoir between K, and h, is filled with gas at low pressure, with residual oil, and with interstitial water. If at a time t = 0, the level of the oil in the wellbore is lowered to a height h,, what is the production rate from the reservoir at a time to The configuration within the reservoir at some instant

Jan 1, 1957

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

A SPRING meeting is to be held at Cleveland this month under the joint auspices of the Iron and Steel Committee and the Ohio Section with the cooperation of the neighboring sections in Pennsyl-vania, Illinois, and the other States of the Great Lakes region. The discussions will be focused on just one subject, that of manganese, but will cover that thor- oughly as is indicated by the following list of papers. TECHNICAL PROGRAM Some Political Aspects of the World Manganese Situa-tion. By C. K. Leith, Professor of Geology, Uni-versity of Wisconsin, Madison, Wis. Manganese Resources in Relation to Domestic Con-sumption. By J. V. W. Reynders, Consulting En-gineer, New York, N. Y. Manganese Deposits of the&apos; Gold Coast, Africa. By Sir Arthur E. Kitson, Director of the Geological Sur-vey of the Gold Coast, London; with Notes on the Petrology of Certain Associated Manganese Silicate-bearing Rocks. By Maj. N. R. Junner. Reserves of Lake Superior Manganiferous Iron Ores. By Carl Zapffe, Manager, iron ore properties, North-ern Pacific Railway Co., Brainerd, Minn. Iron Manganese Alloys Low in Carbon. By. Sir Robert Hadfield, Hadfields, Ltd., London. Manganese in Non-ferrous Alloys. By M. G. Corson, Consulting Engineer, New York, N. Y. Importance of Manganese in the Steel Industry. By H. M. Boylston, Professor of Metallurgy, Case School of Applied Science, Cleveland, Ohio. Minnesota Manganiferous Iron Ore in Relation to the Iron and Steel Industry. By T. L. Joseph, E. P. Barnett and C. E. Wood of the North Central Min-ing, Experiment Station, U. S. Bureau of Mines, Minneapolis, Minn. Representatives of the leading steel companies, the Army, the Navy, the Geological Survey, Bureau of Mines, and leading technical societies will be present and a lively discussion of the various papers is already assured. Nearly 14 pounds of manganese is needed for every ton of steel made. Estimates indicate that the total reserves of ore in this country suitable for making ferro would hardly supply domestic requirements for ten years, even if it could all be mined in that time. The grade of ore called for by present practice must come from abroad. The present tariff policy of this country is stated to cost industry $8,000,000 in order to force production of manganese ore to the extent of $600,000. What is the wise thing to do? Should a stock be accumulated? If so, how? Is it feasible to change practice and use low-grade ore or to beneficiate the ores of this grade and meet our requirements? What progress is being made in this direction? ,These and similar questions are raised in the various papers that have been submitted and will be open for dis-cussion.

Jan 3, 1927

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-&apos; "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~&apos; for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang&apos;s value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- &apos; mole per cal, and a Cdil value of 2.3 x 10&apos; ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-&apos; per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang&apos;s value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-&apos; mole per cal, which is much

Jan 1, 1969

The Inspiration ore body was discovered in 1904, but a 50 -ton mill which was installed to treat the disseminated copper ore promptly failed. The original Inspiration Company then gave way to another, backed by W. B. Thompson, which found 40 million tons of ore. Control then passed to Anaconda and Dr. Louis Ricketts took charge as consulting engineer. He abandoned the mill which had been partially built (to the horror of the stockholders, according to Ira Joralemon) and spent a year and a million dollars experimenting with flotation. The first large copper flotation plant was then built and recovered 50% more copper than had previous gravity mills. It, of course, was highly successful and became the forerunner of modern flotation plants. Inspiration is distinctive as the first fully integrated copper operation in the United States. Three open pits supply sulfide ore to the concentrator and mixed oxide and sulfide ore to a vat leaching and electrowinning operation with leached ore also being sent to the concentrator. In addition, dump leaching supplies pregnant solution for scrap iron precipitation. Inspiration has recently constructed an electric furnace smelter and also operates a continuous casting and rod plant. The new primary 54 in. by 74 in. crusher was completed in May of 1972 and replaced an older unit which was in the way of the open pit development. It is of an unusual circular silo design, which permits dumping 0 from two positions at 90 from each other. One dumping position is in line with the spider, while the other one is at right angles to it. A box girder splitter bar hung from the dump pocket slopes downward from the second dump point, across the spider cap, and rests on the pocket bottom. This splitter was not installed to protect the spider but was to aid in distributing wet ore being dumped from that position to both sides of the spider. Any large amount of wet ore delivered to one side of the spider would pack in the crusher cavity. The round front wall of the 18 ft (5.5 m) deep pocket is unlined except for light steel protection at the top, while the straight back wall is lined with vertically positioned railroad rails. Water for dust suppression is sprayed into the pocket through a cluster of 3/8 in. (9.5 mm) nozzles at the back of the pocket. About 5 gpm (19 lpm) of water are mixed with 90 psi (620 kPa) air upstream of the nozzles to produce a fog which is effective in dust control. The 54 in. Allis -Chalmers gyratory is placed mostly within one quadrant of the circular enclosure to permit placement of the apron feeder on the lowest level in the proper position to transfer crushed ore to the

Jan 1, 1978

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

In the Ti-Cd system two intermediate phases, TiCd and Ti Cd, have been found and characterized by X-ray diffraction powder techniques. An earlier reference&apos; had reported the existence of the compound Tisd. No structural details, however, were given nor was there any indication of the possible existence of other binary compounds. Studies of the solubility of titanium in liquid cadmium2 led to the discovery of both TiCd and Tisd. The solid phase in equilibrium with saturated solutions of titanium in liquid cadmium at temperatures below 620°C is TiCd, whereas TizCd is the equilibrium solid phase above 620°C. Both thermal analysis and X-ray studies show that a peritectic reaction between the y phase (~isd) and cadmium to form the 6 phase (Ti Cd) occurs at 620°C. X-ray diffraction powder photographs of material isolated from the ingots used in the solubility measurements as well as material prepared by a direct heat of the appropriate stoichiometric amounts of titanium and cadmium can be indexed on the basis of a tetragonal unit cell with a = 2.904 ± 0.002A, co = 8.954 * 0.004A, c/a = 3.083. No variation of lattice parameters indicative of a range of composition is evident. With four atoms in the unit cell the calculated density of the intermetallic is 7.05 g per cm3; the observed value is 7.07 g per cm3. The TiCd lattice is primitive as indicated by the fact that there are no systematic absences among hkl reflections. The absence of all hko reflections for which h + k = 2n + 1 is also evident. This systematic absence indicates the following two space groups, C\h — P4/n and D&~4/nmm; both groups, however, have the same two- and four-fold positions. Stoichiometry, symmetry and space group indicate two likely structure types. They are the PbO-litharge3 (B10) type and the Ti CU (B11) type. Spatial considerations favor the B11 structure with atoms placed in the following positions: 2Ti (c) 0, 1/2, Z; l/2, 0, Z 2Cd(c) 0, 1/2, Z; 1/2, 0, Z The TiCd structure may be summarily described as a layered structure in which double cadmium layers alternate with double titanium layers along the c-axis. The best agreement between calculated and observed intensities is obtained for the values ZTi = 0.608 and ZCd = 0.130. Calculated and observed powder intensities as well as other pertinent powder data are recorded in Table I. Interatomic distances for the proposed structure are recorded in Table II and are to be compared with the distances of closest approach for titanium and cad-

Jan 1, 1962

By J. R. Cahoon, W. V. Youdelis

In a recent publication by Flemings and Nereo, equations for the calculation of the solute distribution in castings were developed, and the solute distributions for unidirectionally solidified A1-4.5 pct Cu ingots cast under various thermal conditions were calculated. The equations derived by Flemings and Nereo for the dendrite "expansion" and "steady-state" zones are essentially equivalent to those previously published by Kirkaldy and Youdelis, 16 for, although the flow velocity cooling rate, and temperature gradients appear in the fundamental differential equations, calculation of the solute distribution requires that the above be explicitly related to the assumed or measured solid-liquid mass distributions during solidification. In the treatment of Kirkaldy and Y-oudelis the mass distributions are simply assumed or measured without any prior and explicit association of the mass distributions to a velocity parameter. The treatment of Flemings and Nereo permits solidification conditions more complicated than the simple unidirectional case to be considered (although in principle the treatment of Kirkaldy and Youdelis could also be extended to include the more general solidification case); however, we note some limitations in the treatment of Flemings and Nereo, and the purpose of this discussion is to point these out and also to indicate those points of similarity in the mass distribution models used which make the two treatments equivalent. Both the Kirkaldy-Youdelis and Flemings-Nereo treatments consider a zone of dendrite "expansion" followed by a "steady-state" zone. However, Flemings and Nereo have failed to consider a zone of "collapse" which begins at the base of the first dendrites to reach the top of the ingot. The omission of this zone of "collapse" results in too high a value for the solute concentration in the latter portion of the ingot to solidify and the conservation of total solute is not possible. In the zone of "collapse" the solute concentration rapidly decreases, which may be accounted for as follows: consider a mushy zone of length X,, shown schematically in Fig. 11 (a), which develops at the chill face and then moves as a steady-state configuration along the length of a solidifying ingot. The solute distribution in this zone, when it first attains the steady state, is shown qualitatively in Fig. 11(b). The segregation is positive (above Co) in the region ab because this region contains primary dendritic solid, ranging from kco to kcE in composition (where k is the partition coefficient and CE is the composition of the eutectic liquid), and liquid metal near eutectic composition. The segregation is negative (below Co) in the region bc because it contains primary dendritic solid only slightly above kco in average composition and liquid metal only slightly above Co in composition. As the zone X, moves as a steady state

Jan 1, 1969