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By Norman P. Goss

It is generally agreed that cold-working mechanically refines the grains into smaller fragments and with continued working these are oriented with certain crystallographic directions bearing a relation to the direction in which the metal is worked. Some of the energy expended on the metal during plastic deformation appears in the form of heat, but a very small portion remains in the metal as stored energy. The entropy, specific heat capacity, temperature at which recrystallization will just begin, density, ductility, elasticity, tensile strength, and resistance to corrosion are affected. These properties have been studied extensively and some of the changes in the physical properties due to cold-working were attributed to lattice distortion.l-8 The broadening of the Ka lines on the X-ray diffraction diagrams of plastically deformed metals is believed to indicate lattice distortion, and consequently the existence of internal stresses. The evidence supporting this theory rests solely upon the observed experimental fact that the diffraction lines are broadened and the Ka doublets are completely diffused. Elam9 has reviewed the matter of lattice distortion in relationship to the hardening of metals by plastic deformation. The X-ray diagrams of plastically deformed metals differ in general from annealed metals. The hardening of a metal was believed due to lattice distortion.9 The resolution of the doublet is lost when a metal is cold-worked and the Laue spots are elongated. At one time this elongation was thought to indicate the elastic bending of the crystal planes. However, more careful work showed that the asterism was due to new orientations developed within the fragmented grains during plastic deformation. Some theories attributed the hardening to fragmentation of the grains into smaller units. Jeffries and Archer,ll after carefully considering the problem of work-hardening from many angles, came to the conclusion that cold-working mechanically refines the grains into smaller crystal fragments, some of which at least differ in orientation from the parent grain. The increase in

Jan 1, 1940

By R. N. Stevens

GRAIN boundary sliding plays a part in the high-temperature deformation of polycrystalline solids, and many investigations1-11 have been carried out to determine the deformation contributed by this mechanism. The principal method employed has been to measure one of the components of the grain boundary displacement, see Fig. 1, at a large number of boundaries, and from the mean value so obtained to calculate the elongation contributed by sliding. A formula connecting these mean values and the elongation contributed is evidently required, and many have been derived. They are usually of the form where Egh is the tensile elongation contributed by sliding, is the mean value of the component, x, N is the mean number of grain boundaries intersecting a line of unit length, and K is a dimensionless parameter known as the averaging factor. Table I summarizes the equations used by various investigators. Examination of these shows that their derivations usually involve doubtful assumptions, and are often in serious error. The purpose of this note is to point out that rigorous solutions to the problem of calculating Egb from x have been available in the literature for some years.' Since this is so little known, and also the original derivations do not make some important points clear, it is proposed to rederive the basic equations. These will be extended further, and the conditions in which the extended equations may be applied will be indicated. The mean values of the components of the sliding vector (I, d, and I:, Fig. 1) will depend on the method by which boundaries are sampled in order to make measurements.3,11 Boundaries are usually sampled by marker lines parallel to the stress axis, or lines perpendicular to the stress axis, the measurement being made at the point where the marker line intercepts the boundary. We will denote the mean values determined by these various sampling methods as follows. lT, dT and vT are mean values obtained by making measurements at pointswhere a transverse line intercepts the boundary while lL, dL, and vl, are the mean values from a longitudinal line. The number of boundaries per unit length also may depend on the direction of measurement, and so we define NT and Nl to be the number of boundaries per unit length, after creep, in the transverse and longitudinal directions, respectively.

Jan 1, 1967

By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957

By C. A. Heberlein

C. A. HEBERLEIN,* New York, N. Y.-The results stated by Rey and Brevers are so startling that they are of great interest, as the concentration of a low percentage of cinnabar by differential flotation yields a high-grade concentrate in the presence of either arsenical or iron pyrite. The authors say: "Cyanide can thus be used to depress arsenopyrite and make a good cinnabar-arsenopyrite separation. A cinnabarpyrite separation could probably be effected in the same way." Corrosive sublimate at the present price of mercury would be a very expensive reagent but the expense would be justifiable if a high rate of concentration could be obtained with a high extraction. On my request, special tests were made in the Punitaqui mill in Chile along the line suggested by the authors, without any improvement of either grade or extraction. As the recovery of the cinnabar in a complex sulphide of chalcopyrite and pyrite gave unsatisfactory results, I had tests made at the testing laboratory of the American Cyanamid Co. at Stamford, Conn. As these tests turned out to be highly satisfactory, not only at Stamford but later at the mine, they are presented here. [AMERICAN CYANAMID TEST FEED PER CENT Si02 66.54 A12032.08 CaO0.70 MgO 0.00 Alkalis1.78 Fe15.63 Cu0.44 S9.42 Hg0.45 OZ. PER TON Ag0.95 Au0.151 Screen Analysis of Tailings, Per Cent Plus650.0 Plus 1001.32 Plus 15020.75 Plus 20019.85 Minus 20058.08] The pulp had a density of 22 and a pH of 7.8. Total time of conditioning was one minute. The reagent added was Texas fuel oil, 0.116lb. Of 33.7 Bé. gravity containing 0.9 per cent sulphur. Frother, 0.062 lb. of No. 5 pine oil. Rate of concentration of mercury was 25.7: 1 [ ]

Jan 1, 1941

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano' (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By Floyd C. Kelly

A. HUltgren, .Söderfors, Sweden (written discussion*).—From the results obtained in his own experiments as well as those of Austin and of Grube Mr. Kelley derives a general law, expressed tentatively in the following words: "whenever two metals are brought into intimate contact at a temperature at which diffusion takes place, a comparatively rapid, or abnormal, grain growth results." It is suggested that,, in order adequately to represent the facts, this definition should he restricted by the following qualifications: a and b are the two metals, b diffusing into a. A. At the temperature in question a should exist as phase a 1 having a limited solubility for b. B. The supply of b by diffusion should be sufficient, in view of the rate of diffusion into a 1, to increase the concentration of b above the saturation value in a 1 so as to cause a new phase a2 to form. (7. The phase a2 should have a range of solubility for 6, thus rendering continued diffusion possible. D. In order that the columnar grains may be preserved in the structure the phase a2 should, of course, not suffer transformation on cooling. The phenomenon thus defined may be described as progressive transformation by diffusion. Its mechanism would appear to he as follows: Fig. 17 shows a portion of the equilibrium diagram a-b, Fig. 18 the distribution of b in solution after various periods of diffusion, Fig. 19 represents the structure in cross-section of a cylindrical rod of a at the end of heating period 3. 1. The first effect of diffusion of b into a will be to establish a concentration gradient in phase a1 (1, Fig. 18). When the saturation value for the temperature of the experiment (m, Fig. 17) is reached at the surface, nuclei of, a2 of composition n will form here, and later develop into a continuous layer. Assuming that diffusion proceeds without irregularities and that transformation at any point sets in without lag—i. e., in the moment saturation is exceeded—the transformation a1-a2 will advance inwards on a cylindrical surface concentric with the surface of the rod. The discontinuity of composition at the transformation surface in the position it happens to have at the end of the treatment (3, Fig. 18) will be preserved at room temperature, if the cooling is not particularly slow, and be recorded in the structure as a marked, smooth line, in agreement with Grube's and the author's observations. The shape of the distribution curves in Fig. 18 is also corroborated by the analyses given by Grube. 2. During diffusion, since the secondary phase a2 is always in immediate contact with the saturated part of the primary phase a1, there should be very little lag in the transformation. This means that the first a2 grains formed should grow in preference to the formation of independent nuclei; in other words, columnar growth results. It does not seem necessary to assume, with Green,' whose conception of the phenomenon

Jan 1, 1929

By Wm Price

THE object of this paper is to present a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350° C. throughout the commercial annealing range. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: ALLOY COPPER, LEAD, IRON, NICKEL, MANGANESE, ZINC, PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. PER CENT A 64.68 Trace 0.194 - 6.73 0.06 remainder B 65.82 1.27 0.227 6.17 0.06 remainder C 65.44 Trace 0.345 17.83 0.08 remainder D 65.60 1.08 0.238 17.77 0.06 remainder These alloys were rolled in accordance with regular mill practice to approximately No. 6 B. & S. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately .one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 ½ in. long by ;Z in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 2 1/2 in. were also taken.

Jan 10, 1920

By T. E. Kihlgren, N. B. Pilling, E. M. Wise

Systematic data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541. Introduction The demand for an alloy essentially white in color, which could be cast and worked by simple methods and which possessed strength and corrosion-resisting properties superior to the usual brasses, led to the discovery and early use of cupronickel alloys containing zinc, and sometimes tin, lead and other metals. This type of alloy was generally known as 'German silver until the war, when the term "Nickel Silver" became generally accepted. The element principally responsible for the white color of the alloy and for its strength and corrosion resistance is nickel, which may constitute from 8 to 30 per cent of the alloy. The functions of the other elements will be described later. The manifold uses of nickel silver are largely due to its color, corrosion resistance, ease of casting, fabrication, joining and rather moderate cost. In many instances the alloy is finished by grinding and polishing while in others it may be finished with a silver or nickel plus chromium plate. Electroplates applied to a nickel silver base behave more satisfactorily than those applied to the softer and less resistant alloys, and owing to the white color of the underlying metal the article will retain a pleasing appearance despite local failures of the plating.

Jan 1, 1935

By E. M. Wise, T. E. Kihlgren, N. B. Pilling

Systematic data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541. Introduction The demand for an alloy essentially white in color, which could be cast and worked by simple methods and which possessed strength and corrosion-resisting properties superior to the usual brasses, led to the discovery and early use of cupronickel alloys containing zinc, and sometimes tin, lead and other metals. This type of alloy was generally known as 'German silver until the war, when the term "Nickel Silver" became generally accepted. The element principally responsible for the white color of the alloy and for its strength and corrosion resistance is nickel, which may constitute from 8 to 30 per cent of the alloy. The functions of the other elements will be described later. The manifold uses of nickel silver are largely due to its color, corrosion resistance, ease of casting, fabrication, joining and rather moderate cost. In many instances the alloy is finished by grinding and polishing while in others it may be finished with a silver or nickel plus chromium plate. Electroplates applied to a nickel silver base behave more satisfactorily than those applied to the softer and less resistant alloys, and owing to the white color of the underlying metal the article will retain a pleasing appearance despite local failures of the plating.

Jan 1, 1935

By Philip Davidson, Wm. B. Price

The object of this paper is to present, a survey of some of the physical properties of sheet nickel silver when subjected to cold rolling and when annealed at temperatures extending from 350" C. throughout the coininercial annealing range.. A number of alloys were taken from stock and analyzed. Four of these, representing low nickel and high nickel both with and without lead, were chosen for the tests. The analyses were as follows: Alloy Copper, Lead. Iron. Nickel, ManGanese, Zinc, PeR Cent. Per Cent. Per Cent. Per Cent. Per Cent. PEr Cent. A................ 64.68 Trace 0.194 6.73 0.06 remainder B................ 65.82 1.27 0.227 6.17 0.06 remainder C................ 65.44 Trace 0.345 17.83 0.08 remainder D................ 65.60 1.08 0.238 17.77 0.06 remainder These alloys were lolled in accordance with regular mill practice to approximately No. 6 R. & 6. gage. The bars (which were then coiled) were annealed together in a mill muffle and afterwards pickled in a 10 per cent. sulfuric-acid solution and cold rolled in stages of approximately one number (B. & S.) at a time to No. 18 B. & S. gage. After each stage, suitable samples were set aside for physical tests. Additional samples were chosen for tests after the bars were rolled to Nos. 8, 10, 12, and 14 gage. These samples were annealed together in the mill muffle and, after pickling, were finished on 0.050-in. gage, yielding a series of specimens 2, 4, 6, and 8 numbers hard for the subsequent annealing tests. Tensile test pieces 9 by 1 in. (22.9 by 2.5 cm.) were cut from both lots and the central portion was milled to give a test section 2 1/2 in. long by 1/2 in. wide. A distance of 2 in. was marked off on the edge of each specimen with light punch marks. In the case of the annealed alloys, Erichsen test pieces 4 by 235 in. were also taken.

Jan 1, 1921

By Henry J. Schwellenbach

Lack of a system in scheduling the replacement of capital equipment can result in emergency purchases of units which may later be found unsuitable for the job. New York Trap Rock Corp., which produces crushed stone for use as construction aggregate, was faced with just such a situation some years ago. The company replaced capital equipment only when machinery in use was no longer serviceable, or when there was an obvious need for different equipment. Operating and maintenance costs were generally neglected because an efficient method was lacking. New York Trap Rock has four plants located along the Hudson River, all within 70 miles of New York City. Crushed stone output-6 million tons a year-is moved to markets in metropolitan New York, New Jersey, and Long Island areas by water transport. Customers are contractors with ready-mix concrete and asphalt plants located on the water.

Jan 10, 1959

By H. P. Greenwald

IN the year just passed the Coal Division's Committee on Rock-Dusting reviewed the status of this safety measure in American coal mines and prepared a paper thereon which will be presented at the February meeting of the Institute. This paper supplements one appearing in Vol. 139 of the "Transactions," page 87 (1940). Because that paper will be issued soon, only a summary is given herein.

Jan 1, 1944

By R. Steinitz, J. L. Orehotsky

An analysis was made of the influence of floating molten zone traversal on the purification of tungsten rods and the effect of this purification on the brittle -to-ductile transition temperature. The major impurities detectable in the original rods, i.e., molybdenum and oxygen, were reduced by zone refining from 30 to 3 Ppm. Changes in the trace amounts of other impurities could not be quantitatively determined since they were below the limit of detection. Tensile tests on 3-mil wires, drawn from these rods and recrystallized to 17,000 grains per sq mm, showed a transition temperature of 60°C for the zone Purified and 175°C for the original material. 1 HE brittle-to-ductile transition temperature is manifest mainly in the bee metals, iron,' molybdenum, chromium,3 tungsten,4 and niobium. Since many of these metals cannot be fabricated at room temperature in a commercially pure annealed poly-crystalline state, a considerable amount of work has been done on evaluating the influence of purification on the transition temperature in order to determine indirectly whether the fabricability of these metals can be improved by removing impurities. Smith and Rutherford8 showed that the transition temperature of iron is lowered significantly by zone purification. Working with chromium, Edwards, Nish, and wain7 found also that purification appreciably lowered the transition temperature. A similar evaluation has so far not been reported for tungsten, probably because of the difficulties in obtaining tungsten in a purified polycrystalline state. carlson8 and, more recently, schadler9 have purified tungsten rods by floating zone traversal, but after zone traversal, their rods were single crystals. To obtain high-purity polycrystalline tungsten, a technique has to be round for transforming the zone-purified single crystal material into a suitable polycrystalline structure. The purpose of this investigation was to obtain zone-purified tungsten in a suitable polycrystalline state and then to evaluate the effect of zone purification on the transition temperature.

Jan 1, 1962

By W. C. Ellis, M. E. Fine

WHEN certain binary Fe-Ni alloys are worked cold and then stabilized by a stress-relief anneal, their Young's moduli are nearly invariant over a substantial temperature range determined by composition and work-anneal history.' In the present investigation addition of molybdenum to such alloys (besides increasing the yield strength) was found to diminish the sensitivity of the thermal coefficient of Young's modulus to composition changes. Such alloys are of interest for applications requiring 1 a metal with controlled, low temperature coefficient of Young's modulus and substantial magnetic permeability.' Young's modulus ordinarily decreases with rising temperature. In ferromagnetic alloys a change in modulus on heating due to loss of ferromagnetism modifies the .temperature dependence. Far below the Curie temperature ferromagnetism alters the modulus in two ways: a—Addition of the energy of magnetization, a function of interatomic distance, changes the relation between interatomic energy and distance.' This lowers the modulus in the Fe-Ni and Fe-Ni-Mo alloys of this investigation. b—An applied stress changes the ferromagnetic domain arrangement so that linear magnetostriction contributes to the strain and further lowers the modulUs.~ Since in the alloys of this investigation both effects lower the modulus, loss of ferromagnetism on heating changes the slope of the modulus-temperature curve in a positive direction. With increasing temperature the slope of the modulus-temperature curve, due to progressive loss of ferromagnetism, becomes less negative, goes through zero (the modulus is minimum), becomes positive, and resumes its normal negative value above the Curie temperature.' The increase in modulus and decrease in curvature in the modulus-temperature curve occurring on work hardening have been attributed to a reduction in effect (b).'. Vn the absence of ferromagnetism work hardening through introduction of residual strains would be expected to decrease the modulus.' Alloy Preparation—Test Methods Four series of alloys having nominal molybdenum contents of 5, 7, 9, and 10 pct and containing 47 to 58 pct Fe (the analyzed compositions are given in Table I) were melted in air and cast as bars weighing from 2 to 6 lb. The charge consisted of electrolytic nickel, Armco iron, molybdenum (99+ pct) or ferromolybdenum (62 pct Mo), manganese, and aluminum as a deoxidizer. The bars were swaged cold to the desired diameters with intermediate anneals. Alloys in this composition range are reported" to be face-centered cubic and ferromagnetic at room temperature. The Curie temperatures" decrease with molybdenum. For example, keeping the Ni/Fe ratio at unity and increasing the molybdenum from 0 to 17 pct decreases the Curie tempera- ture from approximately 500°C to room temperature. (The 17 pct Mo alloy requires quenching to retain a single phase.~) Young's modulus at a series of temperatures from —50" to 100°C was determined by a dynamic method previously described.', " In this method Young's modulus is calculated from the resonant frequency (in this case approximately 50,000 cycles per second) of a rod sample (approximately 2 in. long) vibrating longitudinally in the first mode. The densities of the samples at room temperature, Table I, were determined by the standard method of weighing in air and reweighing in redistilled bromobenzene. The linear coefficients of expansion, Table I, needed to calculate the sample length and density at the temperature of measurement, were obtained by observing the change in length (22" to 100°C) of an 8 in. gage distance with a two microscope cathetometer. The values of density and coefficient of expansion in the few samples checked are independent of treatment to the accuracy reported. This was assumed to be general for all the samples. The modulus values are accurate to &0.05x101' dynes per sq cm. However, values of thermal change in modulus are accurate to 20.005~ 10" dynes per sq cm. Young's Modulus Values at 25°C: The modulus values of O', 5, and 10 pct Mo alloys at 25 °C are plotted in Fig. 1 as functions of nickel. After working cold, the samples were either recrystallized at 950" to 1000°C or given a low temperature stabilizing anneal at 400° C. The 400°C anneal does not reduce the hardness nor cause recrystallization. Annealing at 400 °C does

Jan 1, 1952

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active'.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of' gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

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

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

Jan 1, 1960

By Cyril Smith

FOR several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some inter-esting general relationships between the thermal and electrical conductivi-ties for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 ? except for the electrical conductivity at 200° C., which is given in the appendix of this paper.

Jan 1, 1935

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13'14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8'10'12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d'ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By A. N. Winsor

Increased use of private aircraft in civil engineering, mining, forestry, and other land-use activities creates an opportunity for amateur aerial photography. Taking a photograph having less than 5° tilt requires precision equipment and skilled personnel, while controlled horizontal photography is primarily a terrestrial method that has passed to the limbo of forgotten things. But the remaining possibility – oblique aerial photography – can be…

Jan 2, 1955