Search Documents

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

JESSE L. JONES,* Pittsburgh, Pa.-I would like to ask Miss Erskine if down-draft has been used in any of the foundries where heavy fumes have to be removed, instead of the overhead draft.? L. -ERSKINE.-The system of overhead draft to remove heavy fumes has been very much more successful. The entire efforts of the New Jersey Department of Labor in regard to stabilizing conditions in the foundry are the result of the physical examination of the foundryman himself on first-hand information as to the prevalence of the minor ailments and the bad timekeeping that naturally accompanies them. These ailments are a factor in not only increasing the labor turnover but in increasing the percentage of bad work as well. The physical exertion of the foundryman himself is of course an important factor. In certain standard shops the amount of energy expended runs from 11 to 13 tons of foot-pounds of energy a day. In certain shops on piece work, I found a record of the energy expended per day to run as high as 22 tons. In one shop, during the war period, the management established a bonus system, and the men increased their output from 60 to 100 molds a day. The result was an increase of some 60 per cent. in output, and an increase of 400 per cent. in defective castings. The question of the physical exertion in the unsanitary foundries, of course, is very much complicated by other factors, for which reason the department has devoted a good deal of attention to estimating what is a reasonable exertion in a sanitary, well ventilated foundry. We have met certain physical difficulties in the brass foundries that the iron foundries did not have. All that information is available through our Bureau of Industrial Information. The question of the physical energy exerted by the molder is found to have a very distinct bearing on the question of contracts, for the possibility of increasing production is balanced by the extra overhead involved. JESSE L. JONES.-I would like to ask if any evidence has been noticed of carbon-monoxid poisoning among the employees of the foundries.

Jan 4, 1919

By Wallace Ralston

DuRing the year of 1937, the East Texas district produced 211,194,467 hbl. of oil and marketed more than 22,329 million cu. ft. of gas; 3377 oil and gas wells were completed. During this same period 106 exploratory wells were drilled, discovering three new oil fields and one gas-distillate field. Fields East Texas Field.—The East Texas field again led the district as to production and number of wells completed. During the year, 2420 oil wells were completed, making a total of 24,382 producing wells, which produced 171,336,854 bbl. of oil, for a total of 1,156,352,834 bbl. since the beginning. During the year the average bottom-hole pressure dropped 49 lb., making the average bottom-hole pressure 1119 lb. Approximately 3500 wells are making salt water, 20 per cent of them making over 80 per cent of the water. During the month of December, the daily average production of salt water was 119,000 barrels. Talco Field, Titus and Franklin Counties.—The Talco field produced 9,780,948 bbl. of oil during the year, from 637 wells. During the year 472 wells were completed. All of the wells are pumping and 241 are making salt water. This field has followed a normal development and did not exceed the estimated number of acres reported last year. Rodessa Field, Cuss and Marion Counties.—The Rodessa field was extended about 13 miles southwest into Marion County, which added approximately 4000 acres to the field. During the year 260 wells were completed, making a total of 416 producing wells, which produced 12,646,-970 bbl. of oil. The author was unable to obtain figures for the amount of gas produced. The field has two gasoline plants, which had a daily average of 16,558,000 cu. ft. of gas during December, averaging 0.83 gal. per M cu. ft. As of Jan. 1, 31 wells were making salt water. The bottom-hole pressure varies greatly, depending upon the pay from which the well is producing. The average bottom-hole pressure from the Young

Jan 1, 1938

By P. Niessen, S. J. Bercovici

RECENTLY Aust et al.&apos; proposed a model of non-equilibrium grain boundary segregation based on a vacancy gradient induced uphill diffusion process of solute to grain boundaries. According to their proposal, solute atoms which are attracted to vacancies would, during the cooling of a sample, migrate with vacancies toward grain boundaries (vacancy sinks) and thereby enhance the solute concentration in boundary regions. For solute atoms which are not attracted to vacancies no such boundary solute enrichment would be expected. These concepts were given experimental support by boundary and bulk mi-crohardness measurements of various thermally treated dilute zinc and lead alloys and also doped aluminum oxide. The underlying assumption in their work was that solute enrichment in boundary regions is indicated by higher microhardness values. From thermodynamic considerations1&apos;2 it appears that the solid-liquid solute distribution coefficient (K), defined as the concentration of solute in the solid to the concentration of solute in the liquid at equilibrium, indicates whether attractive or repulsive forces exist between vacancies and solute atoms. K < 1 indicates a solute-vacancy attractions, K > 1 indicates no, or a repulsive, vacancy-solute interaction. This note is to report on observations of different grain boundary etching phenomena in high purity zinc alloys. These phenomena appear to depend on whether a K < 1 or K > 1 solute is present. In experiments designed to measure directly the solute enrichment in grain boundary regions, samples of zone refined zinc with 0.1 at. pct solute additions were cooled from 380°C at a rate of 3°C per min. A surface layer of approximately 50 was then removed from the samples by chemical polishing. The samples&apos; surfaces were then protected by a chromating treatment such that in a subsequent etch only grain boundary regions were dissolved. The dissolved regions were approximately semicircular troughs, 10 µ in width. The grain boundaries were usually in the middle, i.e., at the bottom, of this trough. For zinc containing the K < 1 solutes cadmium and aluminum, the grain boundary was always indicated by a ridge as shown in Fig. 1. For pure zinc, and zinc containing the K > 1 solutes copper and gold, a groove at the bottom of the trough indicated the boundary position, Fig. 2., To test if these different grain boundary etching behaviors were possibly connected with the segregation process discussed above, the Zn-Cd alloy was again heated to 380°C and quenched into brine. After surface protection and etching it was found that this specimen no longer exhibited the grain boundary ridges but rather grain boundary grooves as shown in Fig. 2. It would appear, therefore, that the boundary ridge is a consequence of a process occurring during the slow cooling of the samples. From absorption spectrophotometric analysis it was found that for slowly cooled samples containing K < 1 solutes, the solute/zinc ratios of the material from the boundary trough were consistently considerably higher than the solute/zinc ratios of the bulk alloys. This boundary region solute enrichment was not observed in quenched samples. It is concluded therefore, that the boundary ridge shown in Fig. 1 is directly or indirectly connected with nonequilibrium solute segregation.

Jan 1, 1970

IN GATHERING material for this chapter on Yerington and the one to follow on Silver Bell, the A.S.& R. project near Tucson, Arizona, I was fascinated at the way the two stories paralleled each other. For example, here are a few instances: (1) The first copper mining in the Yerington district of Nevada was in the late 1860&apos;s; the first in the Silver Bell area in 1873. (2) Each district was served by a branch railroad about 25 miles long from a main line of the Southern Pacific (by quizzical coincidence); and, in each instance, the railroad was later abandoned and torn up. (3) Each district had a sizable blast-furnace smelter ten or fifteen miles from the principal mines, and in each instance the smelter was later dismantled for junk. (4) Up to 1954, the Yerington district was credited with a production of 100,000,000 lb of copper; the Silver Bell district with 80,000,000 lb. (5) In each district the entire production had come from deposits other than the low-grade ore bodies now being exploited. (6) In each instance, existence of the low-grade deposits of the Porphyry type was recognized in the period circa1910-1914 and a substantial amount of exploratory drilling had been done, on one deposit at Yerington and on two at Silver Bell. (7) In each instance, the properties containing the Porphyry ore were acquired by a strong company (Anaconda Copper Mining Company at Yerington and American Smelt-

Jan 1, 1957

By Wei-Kao Lu

A general rate equation is derived for gas -solid reactions in metallurgical processes by considering the contributions of chemical reaction at inter-phase boundaries and diffusion through the solid product layer simultaneously. This equation takes care of the whole range continuously from purely diffusion control to purely chemical reaction control. The parabolic law,&apos; McKewan&apos;s equationa derived with the assumption of interface area control and the equation derived by Kawasaki et al. with the assumption of purely diffusion control are found as the limiting cases of the corresponding forms of the general rate equation. Many metallurgical processes involving gas-solid reactions have been extensively studied. The common examples of these processes include the reduction of oxides to metallic products, the roasting of sulfides to oxides or chlorides and the oxidation of metals. Gas-solid reactions consist of at least two kinds of steps; one involves the transport of reactant and product to and from the reaction zone and the other is the chemical reaction taking place at the interphase boundaries. In the limiting cases one or the other of the above mentioned steps will be much slower than the other and is then rate controlling. For example, the oxidation of metals is diffusion controlled and obeys the parabolic law.&apos; On the other hand, if the diffusion rate is much larger than the chemical reaction rate then it will be controlled by the chemical reaction rate. This latter case occurs for the reduction of iron oxides studied by McKewan. If the rate of diffusion and of the chemical reaction have the same order of magnitude, a more detailed analysis is necessary. Thus at the beginning of the reaction when the solid and gaseous reactants are in direct contact, the reaction should be chemical reaction rate controlled as no diffusion process is involved. At the other extreme as the reaction zone moves further into the solid, the diffusion distance becomes greater and the diffusion rate continuously decreases. Eventually, therefore, for a sufficiently large sample the rate must become diffusion controlled. As the transition from one controlling step to the other must be continuous, we cannot describe this transition period by either of the two limiting cases. In this paper the author attempts to derive a general rate equation for gas-solid reaction systems. This is effected by considering the rates of diffusion and chemical reaction simultaneously from the state of pure diffusion control to pure chemical reaction control. I) DERIVATION The system under consideration is made of at least three phases, namely the gaseous one, the solid reactant, and the solid product as shown in Fig. 1. The notations are listed at the end of the paper. The mass transfer process involves the diffusion of reactants and products across the solid product layer. It is reasonable to consider that no chemical reaction will take place in the solid product layer with respect to both gaseous reactant and product. For the characteristics of local equilibrium of the system, the diffusion process is really in a quasi-steady-state. It will be proved in the following paragraphs. Then we can invoke the law of conservation of mass valid for all chemical species passing through the layer. The solid reactant sphere has an initial radius, ro, after a fraction of completeness of the reaction, the unreacted core has a radius ri, where r, is in the solid product region. Let Cg be the activity of gaseous reactant in the

Jan 1, 1963

By L. D. Hall, D. R. Mash

The paper presents the results of experiments on the anelastic. behavior of gold, as manifested by grain boundary relaxation. Two grain boundary internal friction peaks are found for 99.9998 pct Au. It is found that the peaks are associated with primary and secondary recrystallization. However, the existence of two discrete peaks cannot be explained on the basis of grain size and shape alone. It is suggested that grain boundary stability, as determined by orientation, plays a role in the observed effects. EVIDENCE for the viscous behavior of grain boundaries in metals has been presented in recent years by several investigators, based upon studies of various anelastic effects, especially internal friction. KG1 has contributed greatly to this field, having put forward a coherent body of evidence for stress relaxation by the viscous intercrystalline flow mechanism. In this connection, he has made extensive use of pure aluminum (99.991 pct) as the test material, although he has also studied other metals and alloys, including pure iron (Puron).² Rotherham, Smith, and Greenough³ have studied the internal friction of pure tin, interpreting their results in a manner similar to that of KG. In view of the importance of such studies in shedding light upon the fundamental structure and behavior of the grain boundaries in pure metals, it appears that the use of a very pure test material which is inert to its environment should provide useful information on anelastic properties and the source of such behavior in pure metals. The present work was carried out on spectrograph-ically pure, 99.9998 pct Au, free of all impurities except for a trace of silver, estimated to be present to the extent of about 0.0002 pct. The term "pure gold" will hereafter refer to this very pure material. Gold of commercial purity, 99.98 pct, was also studied to observe the effects of small amounts of impurities. A pure gold "single crystal" specimen was also tested for comparison. The variation of the internal friction and rigidity modulus as a function of temperature was determined by means of a torsion pendulum apparatus employing extremely low stress amplitudes and a frequency of vibration of the order of 1 cycle per sec. A 12 in. length of 0.031 in. (20 gage) gold wire formed the suspension element. The apparatus was similar to that described by Ke.l The test procedure and the basic requirements to be met for obtaining useful experimental data by this method have been given elsewhere.1,2 It should be made clear that in all of the experiments to be described, the internal friction and rigidity were independent of the amplitude of torsional vibration. The semilog plot of amplitude of vibration vs ordinal number of vibration was a straight line. This was carefully verified for each internal friction measurement. The linear variation shows that the internal friction was independent of stress; i.e., that the specimens were not being cold-worked during testing. The reproducibility of the internal friction curves, which were obtained by cyclic heating and cooling, indicates that the gold was unaffected by its environment during the tests. The measure of internal friction adopted in the present study is the conventional "logarithmic decrement," defined as follows: log. dec. = l/n In A0/An [I] where n is the number of cycles or vibrations; A,, the initial amplitude of vibration; and An, the amplitude after the nth cycle. When the logarithmic decrement is small, the shear modulus, G, of the wire is proportional to the square of the frequency of vibration provided the length and radius of the wire are kept constant. A plot of frequency squared vs temperature gives the following ratio:&apos; This expresses the fraction of the stress which has not been relaxed at a given temperature. Gr and Gv are the relaxed and unrelaxed moduli, respectively. The frequency of vibration in the polycrys-talline specimen is fp, and the frequency of vibration of a single crystal is f8. This latter quantity is obtained simply by extrapolating the linear, low temperature portion of the curve of frequency squared vs temperature for the polycrystalline specimens. The theory of viscous grain boundary stress relaxation as demonstrated by the anelastic behavior of metals has been discussed in detail by Zener4 and need not be reproduced here. Experimental Results Initial measurements of the internal friction of pure gold were carried out on specimens which had been drawn with no intermediate annealing, resulting in a material which had undergone approximately 99 pct reduction of area in final processing. Annealing was then carried out at successively higher temperatures starting at 400°F for 1 hr and proceeding in this manner to as high as 1600°F in 100°F intervals. After each annealing treatment an internal friction and rigidity vs temperature curve was obtained over the range from room temperature to the particular annealing temperature. The resulting internal friction curves did not exhibit well defined maxima (peaks), but rather several fairly flat

Jan 1, 1954

By M. E. Wadsworth, J. R. Lewis, J. M. Quets

Samples of snythetic magnetite were reduced in hydrogen at various partial pressures and temperatures. The reaction mas found to be surface controlled and directly proportional to hydrogen partial pressure over the temperature range studied (400° to 1000°C). A transition in the mechanism occurred at approxirnately 590°C. This has been attributed to a change in the slow step of the reduction reaction resulting from the presence of stable wüstite at higher temperatures. Below 590°C the heat of activation for the reduction was found to be 14,700 cal per mole and it was 3,200 cal per mole above 590°C. THE reduction of the oxides of iron has been a subject of study and interest for many years. Edstrom1 has reviewed the work up to 1953 and his findings provide much basic information concerning details of the reduction of hematite (Fe2O3 ) and magnetite (Fe3O4) with both H2 and CO. He concluded that below 600°C the reduction of both hematite and magnetite was essentially identical, since the rate was controlled by a surface reaction at a magnetite gas interface and the iron formed was very porous. The decrease in the reduction rate for both hematite and magnetite immediately above 600°C was attributed to the formation of a stable wüstite phase across which diffusion was very slow. The wide difference in reduction kinetics for hematite and magnetite above 600°C was explained in terms of the character of the wüstite formed. The rate of magnetite reduction increased slowly with temperature beyond the minimum immediately above 600°C and rates equivalent to those observed at 550°C were not obtained until the temperature was increased beyond 850oC. Edstrom and Bitsianes2 studied the solid-state reduction of magnetite, the reaction of which can be written (4x-3)Fe + Fe3O4—4 FexO [1] where x is between 0.83 and 0.95. The rate was found to be controlled by the kinetics of transport of iron ions through the wüstite phase. Bogdandy and Riecke3 studied the kinetics of reduction of small grains of iron oxide in hydrogen and qualitatively attributed the slow step in the reduction process to the diffusion of hydrogen and water vapor through pores. McKewan4 has analysed the data of Joseph,5 Stalhane and Malmburg,6 and Lewis7 and has demonstrated that the kinetics of reduction of both hematite and magnetite are controlled by surface reactions and also that the variation in surface area during reduction must be accounted for. McKewan was able to correlate the reduction data by the equation rodo[1-(1-R)1/3] = Kt [2] where ro is the initial particle radius, do is the density of the iron oxide, R is the fraction reduced at time t, and K is a rate constant. The applicability of Eq. [2] for temperatures above 600°C where a stable wüstite phase is present, indicates the slow step in the over-all kinetics does not result from diffusion unless diffusion occurs laterally along the oxide metal interface or through a wüstite layer of constant thickness. Diffusional control through a layer of wüstite is unlikely, however, in view of the pressure effects demonstrated by Tenenbaum and Joseph,&apos; Diepschlag,9 McKewan,10 and the results of the present study. McKewan has demonstrated a linear rate dependence on the hydrogen partial pressure over the temperature range 400" to 1050°C for the reduction of hematite.

Jan 1, 1961

Jan 1, 1915

By Taylor Lyman, E. P. Klier

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.&apos; Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

By E. P. Klier, Taylor Lyman

The structures formed when austenite is quenched to subcritical temperatures and allowed to transform isothermally have been the subject of intensive study since the work of Davcnport and Bain.&apos; Isothermal transformation diagrams summarizing the results of many of these studies have become widely familiar to metallurgists. Of particular interest to metallographers are the dark-etchingl acicular products of transformation formed by isothermal reaction below the temperature of maximum velocity of the austenite to pearlite reaction. These products, the bainite structures, can he formed in a wide variety of steels. However, the constitution of bainite is not well understood and divergent views have been expressed as to its mode of formation. In this investigation a combination of dilatometric, microscopic and X-ray methods has been brought to bear upon the problem in the hope of some elucidation of the bainite reaction as it occurs in hypo-eutectoid steels. Mechanism OF Bainite Formation Davenport and Bainl considered the mechanism of bainite formation to consist of two steps—an allotropic transformation followed by precipitation of carbide. The separation in time of the two processes was considered to be very slight in the upper temperature range and very marked at temperatures just above the martensite range. This concept has been restated by Vilella, Guellich and Bain2 in the form of a definition of the acicular mode of transformation as: The successive, abrupt formation of flat plates of supersaturated ferrite along certain crystallographic planes of the austenite grains; this supersaturated ferrite begins at once to reject carbide palticles, (not lamellae), at a rate depending upon temperature In effect, this is the acicular mode of transformation, even though the temperature be such as to limit the actual life of the quasi-martensite to millionths of a second. The investigation of isothermal decomposition of austenite in certain alloy steels (notably those containing chromium or molybdenum) has revealed that there may be a range of temperatures between the pearlite and bainite reactions in which the austenite decomposes at a relatively low rate.3-6 Further, it is characteristic that in the second region of fast reaction the decomposition of the austenite is incomplete by one reaction but goes to completion by a second reaction. These observations led Wever7 to a description of the bainite reaction as follows: I. The reaction takes place by initial precipi. tation of a martensitic intermediate structure. 2. In the upper temperature range this structure readily decomposes into ferrite and cementite. In the lower range carbon separates in an unknown form. 3. In the upper temperature range the precipitated carbide nucleates the precipitation

Jan 1, 1944

J. D. Fast and J. L. Meijering (Philips Research Laboratories, N. V. Philips&apos; Gloeilampenfabrieken, Eindhoven, Netherlands)— After the departure of our friend Dijkstra to the United States, investigations on the effect of alloying elements on the behavior of nitrogen in a iron were continued in Eindhoven. We too found internal friction curves with two separate peaks for iron containing nitrogen in addition to 0.5 atomic pct V or 0.5 atomic pct Mo. Our first publication on these investigations" appeared almost simultaneously with the paper now under discussion. At first sight our experimental results seem to be in harmony with their conclusions, but a closer examination reveals that in the case of the Fe-V-N alloy the abnormal peak is not controlled by one time of relaxation only. Whereas iron containing 0.5 atomic pct Mn or Mo absorbs an amount of nitrogen of about the same magnitude as that absorbed by pure iron under identical conditions, iron containing vanadium absorbs in addition one nitrogen atom for every vanadium atom. This last amount, far exceeding the first amount in the case under consideration, combines chemically with the vanadium and causes no internal friction. The "free" nitrogen in the vanadium alloy gives rise not only to a damping peak corresponding to that in pure iron but— due to the presence of VN particles in the metal—also to the abnormal peak at higher temperatures. The VN particles create interstitial sites around themselves where the free nitrogen atoms are bound much tighter than in the normal interstices. These abnormal interstices, therefore, will capture free nitrogen atoms rapidly, whereupon these give rise to the abnormal damping. The binding energy in the abnormal interstices is not the same for all, and with coarsening of the VN precipitate the distribution of these energies is displaced toward the side of stronger binding. This is deduced from a shift of the summit of the second peak toward higher temperatures (from 80" to 88°C in our experiments) caused by prolonged heating at 950°C. From the intermediate state where they cause the abnormal damping, the nitrogen atoms pass over rather rapidly into the fully precipitated state (iron

Jan 1, 1954

By Emby Kaye

It is the purpose of this paper to outline briefly some of the considerations that enter into the economics of so-called recycling, the generic designation of the relatively recently developed process by which a condensate† is separated from gas-distillate gas at high pressure and the residual gas returned to the reservoir. This subject necessarily embraces not only a discussion of factors that should be considered in projecting a recycling operation, such as estimating reserves, investment and operating costs, but also a comparison of condensate with other types of petroleum. The place of condensate in its relation to the total supply of crude oil is pointed out as well as certain logical methods of product disposal. The cost of drilling wells and lease maintenance is not pertinent to this discussion because income and revenue are in this paper confined to that retained by the plant or plant operator for supplying processing facilities for the gas. Before the development of recycling a great many gas-distillate gas fields in Louisiana and Texas provided no income to their owners. When gas was sold from these reservoirs it was accompanied by irretrievable losses of condensate in the formation. The understanding of the func- tion of retrograde condensation resulted in the introduction of a new commercial petroleum recovery process for these hitherto unexploited fields and now permits the conditioning of this type of wet gas field for the sale of dry gas therefrom without waste. Some Economic Factors The study of a gas-distillate field for possible exploitation necessarily involves the critical appraisal of a number of elements, chief of which will be discussed here: (I) estimate of distillate in place, (2) estimate of distillate that can be brought to the surface, (3) available market, (4) costs. The considerations affecting the estimating of distillate reserves in place are in the main subject to the same errors as are involved in determining dry gas reserves. Determinable data including acreage, sand thickness, reservoir pressure, reservoir temperature, porosity and connate water provide the basis for calculating the volume of gas in place. Ample allowance must be made for connate water, which may occupy from 20 to 35 per cent of the pore space of the sand. The factor of supercom-pressibility is to a considerable extent nullified by the reservoir temperature. It has been considered well advised to allow this factor to serve as a cushion. With the gas reserves calculated, it remains only to assay the distillate content of the gas. Those familiar with the handling of "wet" gas at high pressure readily appreci-ate the variables in sampling gas from

Jan 1, 1942

By Emby Kaye

It is the purpose of this paper to outline briefly some of the considerations that enter into the economics of so-called recycling, the generic designation of the relatively recently developed process by which a condensate† is separated from gas-distillate gas at high pressure and the residual gas returned to the reservoir. This subject necessarily embraces not only a discussion of factors that should be considered in projecting a recycling operation, such as estimating reserves, investment and operating costs, but also a comparison of condensate with other types of petroleum. The place of condensate in its relation to the total supply of crude oil is pointed out as well as certain logical methods of product disposal. The cost of drilling wells and lease maintenance is not pertinent to this discussion because income and revenue are in this paper confined to that retained by the plant or plant operator for supplying processing facilities for the gas. Before the development of recycling a great many gas-distillate gas fields in Louisiana and Texas provided no income to their owners. When gas was sold from these reservoirs it was accompanied by irretrievable losses of condensate in the formation. The understanding of the func- tion of retrograde condensation resulted in the introduction of a new commercial petroleum recovery process for these hitherto unexploited fields and now permits the conditioning of this type of wet gas field for the sale of dry gas therefrom without waste. Some Economic Factors The study of a gas-distillate field for possible exploitation necessarily involves the critical appraisal of a number of elements, chief of which will be discussed here: (I) estimate of distillate in place, (2) estimate of distillate that can be brought to the surface, (3) available market, (4) costs. The considerations affecting the estimating of distillate reserves in place are in the main subject to the same errors as are involved in determining dry gas reserves. Determinable data including acreage, sand thickness, reservoir pressure, reservoir temperature, porosity and connate water provide the basis for calculating the volume of gas in place. Ample allowance must be made for connate water, which may occupy from 20 to 35 per cent of the pore space of the sand. The factor of supercom-pressibility is to a considerable extent nullified by the reservoir temperature. It has been considered well advised to allow this factor to serve as a cushion. With the gas reserves calculated, it remains only to assay the distillate content of the gas. Those familiar with the handling of "wet" gas at high pressure readily appreci-ate the variables in sampling gas from

Jan 1, 1942

By R. G. Hall

An article on the subject of electrolytic zinc no longer needs to be preceded by an apology. The production of zinc by electrolysis is past the laboratory stage and has become an economic factor of considerable importance in the total production of zinc in the United States. The various methods of procedure to be followed fa the greatest economy of manufacture are fairly well known, consequently a detailed description of any method is no longer necessary or desirable. In this paper I shall endeavor to lay down some of the governing conditions in this industry, the relation of methods to ore deposits, freight rates, and sources of power supply. Power Points Assuming for a moment that, for the present at least, the electrolytic production of zinc will be confined to Those localities having developed water power, a glance at these powers so developed in the United States, with their relation to known zinc orebodies of economic size, will not be without interest. Northwest In the Northwest we have water powers, developed and undeveloped, . in Washington and Montana. These must, of course, bear a close relation to the rapidly growing zinc production of the Coeur d&apos;Alenes and of the Butte districts. In general, the power of the territory in question is relatively low-priced, at least as compared with the cost of developing power from coal, and the near neighborhood of large bodies of more or less complex zinc ores makes these water powers of more than usual interest. The same remarks may be applied equally to the developed water powers of the Canadian side of the line in the Northwest, where we have again commercially available complex ore deposits such as are being exploited today at and near Trail. California One of the large complex ore deposits of the far West is to be found in Shasta County in the immediate neighborhood of the territory of the

Jan 1, 1918

By W. W. Anderson, S. Razi

Electroluminescetrce of single crystals of terbium-(loped ZnS prepared by vapor-transport technique shows the sharp line specirum characteristic of the 4f— 4ft,ansitiotzs of the trivalent Tb3 rotz. V-I tt~easuverr~ents give evidence of space-ellarge-lirrlited curvent but the thrveshold for trap-filled law behavior is not iu agreement with Lampert&apos;s theory for. Single injection. Variations of &apos;brightness with applied voltage, the observation of double peaks its brightness because joms, and the spatial distribution oi electroLur?zir~escerrce indicate that the accelet~atiotz-collision mechanism involving the bst lattice and/ov shallow traps is most likely to be responsible fov excitation of&apos; electrolnminescence. Efficiency rtreusuver)~etits show the quantwn efficiency to be about 10 pct and powev efficiency about 0.05 pct. Effect of anr~eallng the crystal in sulfur vapor is to enluztzce llle rare-earth emission. It rs pvoposed tlzat sulfitv anr~ealing crreates acceptorr-lvpe defects with which the donor-type vare-eavtll ion can associate more readily vesulting in enhanced rare-earth emission. A&apos;o such e~zlznr~cerr~etrt is obserued when the crystal is atztrealetl in zinc vapor. Photolianinescence of ZnS doped nith a variety of rare earths also shows tile slurvp l~rze rwve-eavtlz erriission which in sorrretirr~es accompanied by broad band, stvuctureless lattice emission. Photo-atrd electrolutr~itzesce?~ce of ZIIS:Tb slw~rj do!rlit~unt rare-earth emission in the ~ticirzity of 54(3OA corre-sporrdit~g to the transition D* — Fj. Hoz~!el)er, the detailed line structuve of the luo spectvtr is cliffevet~t, irzdicutit~g that different sites are active in the two processes. Decay of rave-eartlr fluorescence in ZnS doped with any of sei!evul vuve eurtlzs car1 be described by a single exporleritial e.scepl joy ZrlS:lIo. Tl~is exceptiotr can be explaitred it~ tevrr~s of tlre closely spaced er~evgy 1e1:els Jov the HO~&apos; iorr. Decay lime measurertzekzts jov ZnS:Tb, using pulsed elect,-ical ar~d pulsed opticcll excitutiorzs, (11-e itz goor1 agrcetrier~t. LUMINESCENCE of rare-earth-doped materials has been a subject of interest for the past 20 years. Within the past few years there has been a considerable increase in rare-earth research motivated in search of new and more efficient laser materials and also due to the use of certain-rare-earth compounds in the preparation of color television screens. The purpose of this study has been to seek an understanding of some of the basic processes involved in exciting the rare-earth luminescence which is associated with transitions within the 4f shell of the trivalent rare-earth ion. Single crystals of ZnS doped with a variety of rare-earth ions have been prepared by vapor-transport technique described elsewhere.&apos; Photoluminescence was excited by a high-pressure short-arc mercury lamp together with suitable glass and chemical filters. For electroluminescence, sinusoidal and pulse excitations were used. 1) ELECTRICAL CHARACTERISTICS 1.1) V-I Measurements. Electroluminescence experiments were performed on crystals of terbium-doped ZnS. The samples were cleaned and etched and indium or In-Ga alloy contacts were alloyed on by heating in H2 atmosphere to 600°C for times ranging up to 10 min. Static voltage-current measurements were made on several samples. Fig. 1 shows the results for a typical sample. For voltage V < 20 v, the V-I relationship is linear giving a resistivity of 2.5 x 109 ohm-cm for this particular sample at room temperature. In the range of 20 to 250 v, I varies as V "3 and at still higher voltages (when electroluminescence is visible to the scotopic eye) current varies as Vs up to 600 v, all at room temperature. At 77"K, for V > 200 v, / I vge5 up to 1000 v. The V-I characteristics at room temperature follow reasonably well the behavior predicted by Lampert&apos; for one carrier space-charge-limited current in an insulator with traps although, as shown later, the expression derived by Lampert2 for the threshold for trap-filled law behavior Vtfl yields an unrealistically low value for trap density if we use the experimental value of 300 v for VtfL. Assuming the case for shallow trapping, the transition from Ohm&apos;s law behavior to space-charge-limited behavior occurs at voltage Vtr given by where no = thermally generated free carrier density, L = length of the sample, e = static dielectric constant, 6 = ratio of free to trapped electron densities, e = electron charge. For the ZnS:Tb crystal, L = 0.5 mm, E = 8.3 €0, Vtr - 20 v, and no = 5 x 10&apos; per cu cm, calculated from the ohmic behavior assuming electron mobility of 100 sq cm per v-sec. This results in 9 = 0= As more and more electrons are injected the Fermi level moves up in the forbidden gap toward the conduction band. If we assume a single-energy level for traps (which is not strictly correct, as we will show later), the current voltage characteristic is profoundly affected when the Fermi level crosses the trap level. The traps are now filled and injected carriers can no longer be immobilized in traps. Hence, current rises sharply with voltage. The transition from space-charge-limited behavior to the trap-filled behavior occurs at voltage VTFL given by

Jan 1, 1968

By Clarence S. Ross

INTRODUCTION THIS chapter on the rô1e of physical-chemical processes in ore deposition presents unusual difficulties because it attempts to discuss the theory of processes that are very imperfectly under- stood, but which are among the most fundamental problems now before the student of ore formation. It is generally believed that a great variety of ore deposits are in some way derived from igneous rocks; but we desire to know the mechanism of their splitting off from the parent magma, the physical and chemical character of the material that acts as a medium for transfer from magma to the point of deposition, the manner of deposition, and the methods of replacement and removal of the invaded rocks. This problem is difficult for the field geologist because it concerns forces that for the most part have long since ceased to act. It involves a complex system of which the time for completion extends from the first development of the parent magma through its intrusion, its slow cooling and crystallization, and the final escape of its last residuum, a time probably represented by millions of years. In space the processes extend from profound depths of the abyssal magma which can never be directly observed, through the horizons characterizing deep-seated igneous rocks and ore deposits; those formed at moderate depths; and ends with surficial ones and surface thermal springs. The geologist usually can study the effect at but one of these horizons: he must attempt to fit his puzzle together while seeing but a few parts at a time. Thus he must deal with many isolated phenomena, as if they were the result of many physical and chemical systems; when in fact his problem involves a single exceedingly complex system, and will only be understood when that entire complex system is understood. The geophysicist is handicapped because he must attempt to interpret an extraordinary complex system, involving physical and chemical conditions which he can never hope to duplicate fully, through the study of many exceedingly simple systems.

Jan 1, 1933

By Edward Halse

The occasional occurrence in metalliferous veins of rounded fragments of rock, matrix or ore, lying loose, embedded in clay, or enclosed in some kind of cement, may be attributed to four causes:— I. They have been washed in from the surface, or from an upper portion of the vein.. II. They are of concretionary origin. III. They have been produced by movements in the country-rock or in the walls of the vein. TV. They have been formed in situ, by the upward, downward or lateral flow of water in the vein itself. In this paper the word " conglomerate " is confined to a rock composed of rounded fragments or pebbles cemented together, as distinguished from a " breccia," in which the rock-fragments are angular. * I. Boulders and Pebbles which have been Washed in from the Surface, or from an Upper Portion of the Vein. In this type it is presupposed that the vein at one time communicated by a fissure or open space with the surface, or with the upper portion from whence the fragments have been washed. One well-authenticated occurrence was described long ago by Fournet. Owing, no doubt, to later dislocations in the lode, pebbles from an old alluvium and sands containing titaniferous iron, as well as fragments of wood, were found in a vein at Huelgoet, in France. " Toutes les parties tendres du filon de Pranal ou ces phenome&apos;nes sont les plus prononces ont 6th excaves jusqu&apos;a d&apos;aasez grandes profondeurs par I&apos; impetuosite des torrents, qui out depose la matiere alluviale.&apos;"

Jan 1, 1906

By David J. Dunn

GENERAL NOTES Liner Design for Comminution Liners in crushers and mills are the mechanical link between machine and ore. The way liners transfer energy to media and ore determines to large degree the production rate, liner wear rate, maintenance cost, energy use, and availability of the comminution process. Plant capacity and mineral recovery economics, and return on investment, are thus strongly dependent upon these simple, low cost metal shapes of which so much is demanded. The complexity of dynamic relationships between liner configuration, material properties, ore characteristics, and operating parameters defy simplistic generalization. Rules-of-thumb and axioms of years past fall into disuse almost daily as new analytical methods, assisted by computers and sophisticated control systems, are applied to crushing and grinding processes. Recent literature is well supplied with references citing production benefits that improved liner designs produce. This chapter is intended to review especially promising liner designs and material developments and presents cameo case studies showing the benefits derived from their application to comminution circuits (Tables 1,2,4,5,7). Complete discussions of liner design and wear materials are beyond the scope of this chapter. Norman&apos;s comprehensive studies in references (1) and (2) and Mclvor&apos;s analyses of mill speed/configuration effects (3) are especially useful reading for designers and operators of crushing and grinding circuits. Changing trends in ore, product value, and costs of wear materials, interest, labor, and energy, make ongoing evolution of liner design equally important for existing mines and for projects still on the drafter&apos;s board. Original designs supplied as new equipment must, of necessity, be best estimates. These can usually be improved as operating experience replaces engineering forecasts. Advent of new materials or design concepts such as the Angular Spiral Liners (Korpi (4) ) or Norman&apos;s Bimetallic design (2) offer improvement potential that must be evaluated if a given circuit is to be kept competitive versus others making similar products.

Jan 1, 1982

By Stanley L. Lopata, Eric B. Kula

SEVERAL methods are available for determining pole figures by X-ray means.&apos; The earlier film methods have been replaced by techniques in which the intensities are measured by Geiger counters on an X-ray diffractometerZm7. These methods utilize either flat transmission or reflection samples,214°8 cylindrical specimens,3 or spherical specimens.7 A single transmission or reflection sample will not yield information over the complete pole figure. The cylindrical specimens suggested by Nortod and the spherical specimen of Jetter and Borie7 have the advantage of allowing the whole pole figure to be obtained without any corrections to the intensity for absorption, There is a lower limit to the size of sheet which can be conveniently studied, however, and sample preparation can be rather tedious. Probably the most common method today for determining the complete pole figure is that developed by Schulz. A flat reflection sample is used for determining the pole figure from the center out to about 70". Because of the geometry of the system used, little or no correction for absorption or irradiated volume is necessary.4&apos;6 A separate transmission sample is used for the region near the edge of the pole figure. This procedure requires two separate samples, one of which must be a thin carefully-prepared transmission sample. Furthermore, since the reflection and transmission data are in different arbitrary intensity units, a region of overlap must be obtained, and the intensity data from one set of measurements converted to units of the other. These are serious disadvantages of this method, and they point out the need for a simplified procedure. Since the reflection technique can be used for planes whose normals lie up to about 70° from the sample surface normal, it is apparent that a complete pole figure can be obtained by reflection alone if sample surfaces are cut at oblique angles to the rolling plane Specifically, if a rolled sample is cut so that the normal to the surface formed lies equidistant (54" 44&apos;) from the rolling plane normal, rolling direction, and transverse direction, then complete information for one quadrant of the pole figure can be obtained by reflection from the surface. Fig. 1 shows this oblique surface, as well as the position of the pole of this surface in the pole figure. When a surface has been cut oblique to the rolling plane, the standard polar stereographic net is inconvenient to use, and it would be more desirable to have the center of the net coincide with the pole of the oblique plane. Fig. 2 shows such a net, where the center has been offset 54&apos; 44&apos; to correspond to a specimen cut as in Fig. 1. This net was in effect obtained by rotating a standard polar stereographic net 54" 44&apos; with the help of a Wulff net. With the experimental setup used. a sample can be cut from plate of 1/2-in. thickness or br Gen- erally thinner sheet is under investigation, and a composite specimen must be used. A convenient procedure has been to bond together, using epoxy resin, sufficient sheets to form a cube. These are clamped in a vise, and when dry, the whole vise is rotated and a flat surface ground at the required angle. The sample is then mounted inside a larger steel ring using Koldmount, the backside ground flat and parallel to the approximate desired thickness. The sample is then polished and etched to remove any effects of cold working during grinding. With this method only one quadrant of the pole figure is obtained. Often pole figures show symmetry around the rolling and transverse directions, and any slight asymmetry is due to scatter. Should the pole figure not be symmetrical, four oblique surfaces, corresponding to the four quadrants of the pole figure, would have to be examined. In most cases there is symmetry at least around the rolling direction, which reduces to two the number of quadrants to be investigated. For many purposes all that is required is an average polefigure for the four quadrants. This canreadilybe obtained with composite specimens of sheet material, where sheets Corresponding to each of the four quadrants can be intermixed. The four quadrants can be obtained by considering sheet in the normal position, and by rotatiolls of 180" around the sheet normal, the rolling direction, and the transverse direction. If desired, the whole thickness of the sheet can be used, yielding an average of the surface and interior textures; or the surface material can be removed from each sheet, resulting in a pole figure for the center alone. Eugene S. Meieran of the Massachusetts Institute of Technology has independently developed the same method. His results, adapted to a pole figure goniometer with a specimen spiraler, will be described in another publication.

Jan 1, 1962