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By R. A. Kinzie

THE major operating costs in a cement plant are labor, power, and fuel. The opportunities and methods of savings in labor and power parallel other industries. Because our industry's use of fuel is large and its method of use is unique, the devices adapted for saving fuel are of interest. In normal practice the raw material in the form of a dry powder or a mud is fed to a rotating inclined cylinder where it is dried, calcined, and clinkered. In a Lepol kiln the raw material is rolled up into little balls with water in the nodulizer, fed to a traveling grate on which it is dried and partially calcined and tben to a short kiln where the process is finished. The more usual methods of saving heat have been the use of long kilns with chains in wet process plants and the use of waste heat boilers in dry plants (fig. 1). At the Santa Cruz plant we have used a Lepol system kiln and achieved a fuel 'economy of 4.7 gal per bbl of clinker or about 704,-000 Btu per bbl. This can be compared with our old kilns using the same fuel and raw material which consume 7.8 gal per bbl or 1,130,000 Btu per bbl. These are gross Btu and not the net figures usually used in reports of foreign companies. Our average consumption for 1948 was 708,000 Btu per bbl of Lepol clinker, based on cement sold, and oil purchased. The overall fuel consumption for 1948 was 6.61 gal per bbl. The Lepol system consists of a nodulizer, a grate, and a kiln. There is the usual accessory equipment which is similar to that used in other cement plants. The following description covers the equipment in operation at our plant. The nodulizer is a cylinder 8 ft 10 in. in diam by 18 ft long set on a slope of 1/2 in. per ft, and rotated at about 10 rpm. It is driven by a 50 hp wound rotor motor drawing about 9 kw. The inside of the shell is cleaned by a continuously operating scraper which draws 0.1 kw. The dry raw material is fed to the nodulizer where, being sprayed with water, it rolls into small spheres about 90 pct being between 1/2 and 1 in. in diam and containing about 15 pct water. The nodules fall on the traveling grate where the hot gas from the kiln is pulled down through the

Jan 1, 1951

By B. C. Allen

Grain boundary grooving has been studied in chromium, molybdenum, and tungsten under a variety of conditions using high vacuum techniques and tantalum -gettered argon. The average surface free energy of solid chromium, and the chromium-liquid silver interface free energy were respectively found to be 2200 ± 250 and 500 i 130 ergs per sq cm from groove formation kinetics and estimates of pertinent volume difffusion coefficients. The results for chromium were unffected by variations in interstitial content ranging from 0.003 to 0.09 pct C, or 0.003 to 0.03 pct O. Surface diffusion is the primary mechanism of groove formation in chromium under 1 atm argon at 1200" to 140O°C, and is essentially unaffected by 0.003 to 0.09 pct C, 0.003 to 0.03 pct O , metastable nitrogen contents up to -0.01 pct, and up to 2 torr Ag vapor. At higher temperatures, the major mechanism is volume diffusion in argon or evaporation-condensation in stutic vacuum. Surface diffusion occurs in molybdenum at 0.5 to 0.96 and in tungsten at 0.5 to 0.9 of the absolute melting tempera -ture by a single mechanism, possibly by the migration of single adatoms or vacancies. Results were slightly affected by up to 23 tory Sn vapor, and in molybdenum were essentially unaffected by 0.5 Ti or carbon in the range 0.002 to 0.02 pct. Volume difffusion through the liquid is the mechanism of groove formation in chromium-liquid silver at 1200" to 1400°C and in molybdenum-, Mo-0.5Ti-, and tungsten-liquid tin at 1200" to 2000°C. The solid-liquid interface free energies involved were estimated from grooving kanetics. WHEN a grain boundary intersects a solid surface, a groove tends to form along the line of intersection at temperatures above about half the absolute melting point (0.5 TM). The groove progressively grows by preferential atomic migration either by diffusion or evaporation. Establishment of a groove angle occurs in accordance with the grain boundary and surface free energies involved. The motivation for groove formation is a reduction in the total surface free energy of the system. This study is a continuation of previous work on thermal grooving of chromium, molybdenum, and tungsten.&apos; The temperature ranges were extended, and the effect of metallic and interstitial impurities was evaluated. The results were such that certain interface free energies and surface self-diffusion coefficients were deduced from the grooving kinetics. EXPERIMENTAL WORK Materials and Preparation. As indicated in Table I, the 0.05-0.08-cm-thick chromium, molybdenum, and tungsten sheet used was nominally 99.99 pct after recrystallization. Two lots of molybdenum with about the same analysis, Mo-0.5Ti,* and tungsten were ob- *Alloy compsitions are expressed in weight percent . tained commercially. Extruded chromium rod,&apos; prepared from iodide process crystals, was warm rolled to sheet at 700°C. Sheet of three Cr-0 impurity alloys containing up to 0.03 pct 0 was prepared by warm rolling arc melted, extruded, and swaged rod. Two Cr-C impurity alloys containing up to 0.09 pct C were made by equilibrating unalloyed chromium with a known amount of CH4 for 24 hr at 1150°C in previously evacuated quartz capsules. Chromium containing nominally 0.015 and 0.06 pct N was similarly prepared by equilibration with NH3. The sheet was recrystallized to give a stable grain size about equal to the sheet thickness. Molybdenum and Mo-O.5Ti were recrystallized in a tantalum resistance furnace 1 hr at 1 x lo-5 torr at 2300" and 220O°C, respectively. Tungsten was similarly annealed for 1 hr at 2500°C. Chromium and its impurity alloys were outgassed at 1100°C and recrystallized 1 hr at 1700°C under 1 atm Ar. Except for nitrogen, the impurity content stayed roughly constant. Nitrogen in both alloys was reduced to <0.001 pct. In fact, over 80 pct of the added nitrogen was lost after outgassing at llOO°C and annealing sheet 1 hr at 1300°C in argon in the presence of tantalum. Such a rapid loss can be rationalized since -2 torr N are required for equilibrium with 0.04 pct N in solution,3 while the equilibrium pressure is ~10-5 torr over tantalum at 1300°C.4 The recrystallized sheet was cut into small coupons which were metallographically ground and polished on one side with a minimum of grain boundary relief. The surface roughness was on the order of 0.01 µ. The tin and silver used were nominally 99.999 spec-trographically pure. After being outgassed at 1100°C and equilibrated in a molybdenum crucible for 0.5 hr at 1800°C in argon, the tin contained 3 ppm 0, <0.3 ppm N, and 0.1 ppm H. Following outgassing at 900°C and equilibration in a chromium crucible 1 hr at 1400°C in argon, the gas content of the silver was 1 ppm O, <0.5 ppm N, and 0.3 ppm H. Grooving Under Argon or Vacuum. All specimens were placed in unsealed containers made from rod or sheet of the same alloy, thereby enabling the polished surface to achieve gas-solid equilibrium. The annealing fixtures are shown in Fig. 1. The specimen was placed in a resistance furnace with a tantalum or Ta-10W heating element plus tantalum fixtures or radiation shields. Chromium was outgassed at 1100°C, and molybdenum and tungsten were outgassed at 1900°C to 1 x l0-5 torr or at the grooving temperature, whichever was lower. In vacuum anneals, the specimen was then heated directly to the intended grooving temperature. In argon anneals, 99.996 Ar was admitted

Jan 1, 1970

By R. Kossowsky

BRIDGMAN has listed five possible transitions in bismuth at 25°C which were observed as volume changes. He was unable however to detect the last three transitions by electrical-resistivity changes. Kennedy and LaMori have verified the pressures at the Bi 1-11 and Bi 11-111 transitions. They suggested however that the 125-kbar transition previously reported by Bundy3 actually corresponds to the 90,000 kg per sq cm transition observed by Bridgman.1 Jura4 reported a well-defined drop in resistivity at 92 kbar obtained by a four-lead method. The Bi 111-IV and Bi IV-V transitions have not been reported in any of the above-mentioned references.&apos;-&apos; Bundy3 observed a small dent in the low-temperature boundary of the Bi Vll region which is consistent with the presence of a 111-IV boundary. Zeitlin and Bray-man5 were the only ones to report small but well-defined drops in resistance of bismuth at 44.0 and 63.8 kbar, corresponding to Bridgman&apos;s 111-IV and IV-V transitions, respectively. High-purity (99.99 pct) 0.020-in.-diam 0.5-in.-long bismuth wire was used to calibrate the Uniram tetra-hedral high-pressure apparatus used in the present work. The bismuth phase changes at 25°C were correlated with changes in electrical resistance as a function of pressure. The output of a sensitive bridge constructed of carbon resistors and kept at a constant temperature of ±°C during the measurements was fed to the Y axis of a MoseleyX-Y recorder and the X axis was used for time scans. Specimens were pressurized using a hydraulic press with maximum capacity of 200,000 lb. Load was applied in increments of 2000 lb and held for about 3 min. The resistance was recorded at the end of this time period. Good contact was established below 20,000 lb. Typical recorder charts are reproduced in Figs. 1 and 2 which show that resistance fluctuations were practically nil during each time scan. Well-defined discontinuities in resistance were observed at 58,000 and 82,000 lb, Fig. 1. Two small but definite "blips" are noticed at 92,000 and 122,000 lb, Fig. 2. At 156,000 lb another drop is observed which

Jan 1, 1967

By C. F. Weinaug

In recent years, several methods have been proposed for correlation of physical properties and behavior of hydrocarbon systems. These correlations were found to be unsatis. factory for predicting differential gas liberation and shrinkage data now obtained experimentally. To achieve the desired accuracy, methods were developed to adjust the correlations with two experimental pieces of data. The required data are the saturation pressure at reservoir temperature and the specific volume or density at these conditions. The saturation pressure is used to adjust the vapor-liquid equilibrium-ratio correlations. The density measurement is used to determine the apparent density of liquid methane. With these adjustments, differential gas liberation and shrinkage are predicted within the experimental error. EQUILIBRIUM RATIOS Equilibrium ratios published by the National Gas Assn. of America&apos; were used as a basis for the calculation. The convergence pressure for the sample was determined by using a hypothetical binary system, with methane as one component and the remainder of the system lumped together to form the other component. For the critical temperature of the heavy constituent, the weight average of the critical temperatures of the ethane and heavier components was used. The correlation of pseudo-critical temperature, density and molecular weight of Matthews, Roland and Katzl was used in this calculation for the hexane and heavier fractions. Points for the critical properties of methane and the hypothetical heavy constituent were placed on a chart of the critical loci of hydrocarbon systems. A critical loci for the hypothetical binary system was drawn, and the critical pressure of this system was determined at the reservoir temperature. This critical pressure became the convergence pressure for which equilibrium ratios were read from the NGAA4 charts. The NGAA equilibrium constants for C, through C, were used for the C,; through C, fractions since they were separated on the bases of normal paraffin boiling points. The correlation of Hoffman, Crump and Hocott5 as used to estimate the equilibrium constant for the C fraction. The NGAA eauilibrium-ratio charts are based primarily on paraffin systems and have to be corrected for the presence of naphthenes and aromatics. The correlations in the literature proved too unsatisfactory for determining these corrections. EXperimental data, the saturation pressure, is used with the correlation of Soloman2 to make this adjustment. The correction factors of Soloman were cross-plotted so that the factors for ethane and heavier components were made a function of the factor for methane. a2 = 0.7927 at + 0.1646 .........(1) where a, = correction coefficient for for methane NGAA equilibrium ratio, and a2t = correction coefficient for ethane and heavier NGAA equilibrium ratios. This equation and the equation for the bubble point are solved simultaneously for the correction coefficients. The bubble-point equation is anKnXn = 1.0 . . . . (2) The equilibrium constant for the saturation pressure at reservoir temperature is used. This procedure not only corrects for the relative volatility between components, but also assures that the results will be directly related to the experimental saturation pressure. METHANE DENSITY After determining a set of equilibrium ratios, the apparent density of condensed methane at 60°F and 14.7 psia was estimated. This was found to be necessary because the correlations of Standing3 ere found to be unsatisfactory. The law of additive volumes was employed to make this calculation.

The production of petroleum in India (including Burma) increased from 334,811,624 gal.&apos; ill 1936 to 350,322,222 gal. in 1937, the highest figure in the history of the industry. The increase in 1937 was clue to an increase of some 20 million gallons from Singu, 51/2 million gallons from Attack, 11/4 million gallons from Thayetmyo, and 1 mi1lien gallons from Digboi, accompanied by decrcases of 91/2 million gallons from Yenan-gyaung and 2 million gallons from Yenangyat,. The amount of gasoline produced from natural gas during the year was 10,616,313 gal. in Burma and 456,780 gal. in the Punjab. Yenangyaung Field.—The Yenangyaung field maintained its reputation of being one of the most wonderful oil fields in the world. The total production during 1937 was less than in the previous year but the resources of the field as a whole are sufficient to ensure an adequate supply of oil for many years. At the end of 1037 there were 2910 wells producing in the field. Besides a large number of ells drilled to shallow sands, this total includes 180 hand-dug wells, whose continued existenice is one of the interesting features of the field. During the year the deep drilling activities of 1936 in the southern part of the field died down, owing to the disappointing results obtained. On the eastern flank the limit of present economic extension of the oil sands was approximately demareated. Satisfactory results continue to be obtained from gas drives in the leased blocks; gas is also injected for repressuring and storage. Casing policies continue to be carefully designed to protect the oil sands against the danger of flooding by water and, in general, production methods throughout the field are characterized by a realization of the importance of the conservation of oil and gas and the prevention of waste, whether simple or underground. Singu Field.—-In 1937 the increase in the output from the Singu field was continued. This increased production was due not only to the rapid development of the valuable area in the southern part of the field but also to the successful results obtained from the first wells to produce from behind the practically completed river training wall of the Burmah Oil

Jan 1, 1939

The production of petroleum in India (including Burma) increased from 334,811,624 gal.&apos; ill 1936 to 350,322,222 gal. in 1937, the highest figure in the history of the industry. The increase in 1937 was clue to an increase of some 20 million gallons from Singu, 51/2 million gallons from Attack, 11/4 million gallons from Thayetmyo, and 1 mi1lien gallons from Digboi, accompanied by decrcases of 91/2 million gallons from Yenan-gyaung and 2 million gallons from Yenangyat,. The amount of gasoline produced from natural gas during the year was 10,616,313 gal. in Burma and 456,780 gal. in the Punjab. Yenangyaung Field.—The Yenangyaung field maintained its reputation of being one of the most wonderful oil fields in the world. The total production during 1937 was less than in the previous year but the resources of the field as a whole are sufficient to ensure an adequate supply of oil for many years. At the end of 1037 there were 2910 wells producing in the field. Besides a large number of ells drilled to shallow sands, this total includes 180 hand-dug wells, whose continued existenice is one of the interesting features of the field. During the year the deep drilling activities of 1936 in the southern part of the field died down, owing to the disappointing results obtained. On the eastern flank the limit of present economic extension of the oil sands was approximately demareated. Satisfactory results continue to be obtained from gas drives in the leased blocks; gas is also injected for repressuring and storage. Casing policies continue to be carefully designed to protect the oil sands against the danger of flooding by water and, in general, production methods throughout the field are characterized by a realization of the importance of the conservation of oil and gas and the prevention of waste, whether simple or underground. Singu Field.—-In 1937 the increase in the output from the Singu field was continued. This increased production was due not only to the rapid development of the valuable area in the southern part of the field but also to the successful results obtained from the first wells to produce from behind the practically completed river training wall of the Burmah Oil

Jan 1, 1939

By M. C. Fuerstenau, A. M. Gaudin

Understanding the sedimentation of relatively thick suspensions depends on a knowledge of the concentration of the solids at various positions in the pulp and the times required for thickening. Flocculated kaolin slurries were studied with the transviewer, a device utilizing X-ray absorption in conjunction with a scanning mechanism. A mathematical model based on the Schuhmann size distribution in conjunction with Poiseuille&apos;s law yields experimental filtration rates as a hction of pulp density. These calculations show accord with the experimental results. Accurate predictions of sedimentation results depend upon determining the number and size of pores for given conditions, since the voidage of the suspension controls the volume of liquor that can pass through an element of suspension per unit time. A study on the sedimentation of flocculated kaolin slurries has indicated that their sedimentation takes place by two different processes, dependent on the initial concentration of solids in suspension. One process occurs in dilute suspensions (less than about 2 pct solids by volume) in which a multitude of relatively small flocs settle by hindered settling. In this case, maximal settling velocity is independent of container geometry.1 r2 The other process occurs in relatively concentrated suspensions (greater than about 2 pct solids by volume) in which the mass is considered to be settling as an aggregate network or as one large floc, defined as to size by the dimensions of the container. In this case, container geometry affects sedimentation results significantly. Furthermore, it seems that this single floc is in a state of compression from the beginning of settling, and that two phases of compression settling exist during sedimentation. The first occurs during the early stage of settling where liquid exudes easily and rapidly from the floc, while the second occurs in the compacting portion of the floc where water escapes more slowly and with much more difficulty. Sedimentation of relatively thick suspensions may then be thought to be a filtration phenomenon in which a pulp thickens by the filtration of its contained liquor through the aggregate network of pulp above it. This postulate has also been advanced by others.,4 To understand the sedimentation of relatively thick suspensions more fully, it was felt that knowledge of the concentration of solids at all positions in the

Jan 1, 1962

By B. D. Cullity

GOLD and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,1 this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low- temperature beta form will be considered in this paper. EXPERIMENTAL PROCEDURE The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be pre- pared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsymmetrically in the camera in order to afford a basis for am-shrinkage corrections. A sample homogenized at 5o0°C gave the same diffraction pattern as a sample taken from the as-melted ingot. GENERAL RESULTS The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 ± 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the dsraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an "average" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing some- what more and somewhat less than 50 at. pct gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By A. F. Taggart, Nathaniel Arbiter

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles&apos; of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By Nathaniel Arbiter, A. F. Taggart

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles&apos; of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By B. S. Butler

A. D. Mutch (Falconbridge Nickel Mines Ltd., Ona-ping, Ontario)—This contribution is prompted by the fact that the writer has recently published an article&apos;!&apos; which has in part the same general conclusions as B. S. Butler&apos;s, namely, the form of the standard mineral paragenesis in hypogene deposits and the parallel transition from early high temperature acid to late low temperature alkaline or neutral solutions. Since the writer also recognizes that he is not fully qualified to discuss the formation of ore deposits as a chemical problem, this discussion will be limited to summarizing other observations and will suggest how Butler&apos;s Table II might be made more effective. The form of Butler&apos;s table is not unlike that widely used by European geologists&apos;" in which the various minerals are related to the types of ore fluids—peg-matitic, pneumatolic and hydrothermal. Thus the decrease in temperature and change in pH of the ore-bearing fluids as recognized by Butler may also be paralleled by perhaps even greater changes in composition, density, and character. W. H. Newhouse&apos;s article:" on the sequence of hypo-gene ore mineral deposition is still one of the most complete analyses of the problem. In it he makes four major observations: 1) The order of O, S, As, Sb is the same as their increasing atomic weights and the same as their melting points. 2) The order of the metallic elements is the same as the Schuermann series. 3) The general mineralogical order is paralleled by decreasing heats of formation. 4) The order is generally in decreasing hardness, higher metal content, and higher specific gravity. The order of 0, S, As, and Bi is also the same as their relative abundance. Another point worth mentioning about this series is that As, Sb, Bi, when abundant, often substitute for sulfur in the early pyrite-like minerals, whereas later in the sequence these elements appear to act more like metals. This behavior may be a further indication of the acid character of the early fluids. C. J. Sullivan"&apos; has attempted to show that the sequence of the metallic elements is related to the order of their melting points and has discussed the interrelationship of the different types of bonding of sulfo-phile and oxiphile elements in minerals. Items 3 and 4 might best be summarized by saying that bonding of the minerals in the series appears to be from ionic to covalent to metallic, the early minerals being light in weight, hard, and near-transparent; the intermediate minerals of intermediate weight, semi-transparent, and semi-conducting; and the end minerals heavy, soft, and malleable, opaque and good conductors. A rapid fall in temperature has been assumed to be the cause of ore deposition in many deposits. Perhaps this in turn is the effect of a rapid release of energy in the form of pressure release and change of volume, the first minerals to form being those with the highest heats of formation which absorb the released energy the most rapidly. Butler&apos;s Table II could probably be streamlined and made more effective if the listed compounds were assembled as mineralogical groups as in Dana. Thus the sulfides, arsenides, antimonides, bismuthides, and sulfa salts could be arranged in AX,, AX, A2X2, etc. groups. Since these are continuous substitution series, in which the fields of stability and the heats of formation of the various individual minerals can be fairly regarded as similar, this should be accomplished with no loss of clarity. The occurrence of the individual minerals and the precise sequence of the mineral deposition in any one deposit is probably more dependent on the concentration and relative abundance of the component elements. The assembling of geological data in tabular form such as Butler&apos;s Table II will continue to be a very effective method of studying geological phenomena. The importance of this particular problem has been pointed out by C. F. Park,% who concludes that understanding of mechanisms of the standard paragenesis and interrelated problems of mineral zoning in space and time is one of the major keys to classification of ore deposits.

Jan 1, 1959

By H. l. Burghoff, J. S. Porter

THIS paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 96 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about 10 per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrett1 states the fiber axis of annealed 70-30 brass wire to be [111] with some indication of [100] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. MATERIAL AND PROCEDURE All the wire for the investigation was processed from one. portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02 nickel; 29.83 zinc (by difference). The billet section, 8 in. in diameter, was extruded hot to 3/4 -in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 875°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By W. T. Isbell

In the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 1400O to 1500OF and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace were expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. Equipment and Its Uses Degincing Machine.—The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig 1). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.—The treating chamber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1949

By Y. L. Yao

THE NaT1-type compound may be considered as the penetration of two diamond lattices in such a way that a superstructure of the bcc lattice is formed. Examples of the NaT1-type compound of lithium are LiZn, LiCd, LiA1, LiIn, and LiGa. Except for LiZn and LiCd, each molecule of these equiatomic compounds contains a total of four valence electrons. In LiZn and LiCd it was suspected (for example, see Ref. 1) that the fourth electron was withdrawn from the 18-shell of zinc or cadmium. An incomplete 18-shell would have to show strong paramagnetism. In 1955 Klemm and Fricke2 determined the magnetic susceptibility of LiZn, LiCd, LiA1, and LiIn (also NaTl and NaIn). The molar susceptibility of the outer electrons of LiZn and LiCd was found to be not strongly but weakly positive; that of LiAl and LiIn not negative but weakly positive. Thus they questioned the hypothesis about LiZn and LiCd in particular and the description of the NaT1-type structure in general. However, they did not determine the magnetic susceptibility of LiGa. This note is to report results for all five compounds of lithium. The starting materials are 99.9 pct pure lithium sticks containing less than 0.005 pct Na. 99.9 pct Zn, 99.9 pct Cd, 99.99 pct Al, 99.999 pct In, and 99.999 pct Ga. Weighed amounts of two components were wrapped in tantalum foil and placed in a graphite crucible. It was found that the tantalum sheath minimized the vaporization losses of lithium during melting. The sheath was easily stripped from the alloy rod and the tantalum in the alloy was barely detectable (less than 0.01 wt pct). The melting was performed in a resistance furnace under an argon atmosphere. Alloy specimens were annealed for 1 hr at 400°C in vacuum. The magnetic susceptibility at room temperature was determined by the Faraday Method, using the procedures previously described.&apos; The results are shown in Table I. The interpolated values at 50 at. pct of Li and the average values at 48 to 52 at. pct of Li at 20°C determined by Klemm and Fricke2 are also shown. It is seen that the present value for LiZn and LiCd is slightly more positive but the present value for LiAl and LiIn is slightly less positive than their corresponding values. Also, it is noted there is an abrupt decrease of susceptibility of LiAl from 51.2 to 52.5 at. pct of Li. Klemm and Fricke2 found that the total susceptibility of LiZn, LiCd, LiA1, and LiIn is almost independent of temperature. slater4 gave a working expression for the diamagnetism of the atomic core as follows:

Jan 1, 1964

By W. C. Ellis

Growth directions of tin, zinc, and cadmiun whisker crystals grown spontaneously fi-om the solid are summarized. In tin the edge and diagonal directions of the unit cell are jound with the exception oj- the [110] diagonal. In cadmiurn and zinc the usual dip-ections are a or a + c. The c direction has not been ohserwed. The gvouth directions from the solid are for the most part the same as those found for vapor-grozun crystals and are the ohserz:ed glide directions in plastic j-lou. Whisker crystals of these elements grown from the solid are not twinned. Specular lateral reflections are associated with planes of snall crystallographic indices. WHISKER crystals of tin, zinc, or cadmium grow spontaneously at room temperature in periods from months to years from thin electroplates and other prepared films of the respective metals.&apos;&apos;2 It has been established that these crystals are single, but the question of twinning, such as occurs in whisker crystals of silicon,3&apos;4 has not been resolved. Studies of morphology have been restricted to determinations of growth directions.5-&apos; Whisker crystals are both straight and kinked. A few studies have been made on kinked whiskers including measurements of kink anglesa and determinations of growth directions,&apos; but unfortunately not both on the same crystals. The kink angles, for the most part, for each species are grouped closely about a few unique values, but these values are not always those between observed growth directions in a single crystal. To supplement existing data, the growth directions, identification of lateral features, and presence or absence of twinning were determined with a Weissenberg goniometer by a method described elsewhereg on eight whisker crystals of tin, five of zinc, and five of cadmium. One kinked cadmium whisker was examined in detail. The specimens were needlelike, a few microns in cross section, and of the order of a millimeter in length. They were removed from electroplated substrates on laboratory specimens and commercial equipment after several years of growth as described in Table I. Since the specimens were less than 10 p in cross section they were ideally strong with no attendant risk of plastic deformation or damage in handling. Only deformation twinning has been reported for these elements. Therefore, twinning probably should not be expected in whisker crystals of these metals, particularly a twin plane containing the growth direction. A twin plane oriented in this direction was the one sought in this study. No examination was made for twinning at the boundary between kink segments except for one cadmium crystal. Well-defined reflections occur as a whisker crystal of tin, zinc, or cadmium is rotated about its growth direction when illuminated by a beam of light Although these reflections had been noted in earlier investigations, no study of them was made, probably because the earlier studies had disclosed also that

Jan 1, 1967

By Jean-Jacques Prompsy, J. S. Rinehart

The purpose of the present study was to arrive at a better understanding of the stress fields developed within drill bits under dynamic loading and the influence that these stress fields could have on the failure of the drill bits. Particular emphasis has been given to the influence that bit shape has on the establishment of highly localized, potentially destructive stress inhomogeneities within the bit. This paper covers one phase of a broad study involving three velocity regimes: impacts at very low velocities, 0 to 20 ft/sec, a velocity range in which dynamic effects are just beginning to be found; impacts at velocities ranging from 20 to several hundred ft/sec, arange commonly encountered in practical drilling operations; and impulsive loading through the detonation of explosives, a velocity range in which the dynamic effects are greatly exaggerated and made more identifiable. Specifically, fracturing which develops at the end of a cylindrical bar undergoing a shock produced by impact was experimentally investigated, the impacted area being the face of a truncated cone terminating the cylindrical bar. Fracture characteristics were looked at as a function of impact velocity, area of impacted face and cone angle — parameters of considerable importance in the design of drill bit. EXPERIMENTS The specimens were made of Plexiglas, which enabled the fracture pattern to be easily observed. In Plexiglas, the velocity of a longitudinal wave is about 8,700 ft/sec, and the velocity of the transverse wave about 4,200 ft/sec. The specimens were impacted by a steel cylinder whose lower face was parallel to the terminal face of the experimental bit, as shown in Fig. 1. The impacting mass was shifted up and down on two steel rods, dropping from a maximum height of 11 ft, with the velocity varied between 0 and 6.5 m/sec. The initial mass of the cylinder was 4.1 kg, which could be increased by steps up to 8.8 kg by addition of steel plates. The velocity of the steel cylinder was determined by using an electric circuit; as the cylinder dropped, it contacted two steel wires, the first one starting and the second one stopping an electronic counter. Two similar counters connected in parallel were used to corroborate each other. The velocity was checked at each drop as it had been observed to vary somewhat from drop to drop. The two contact wires were located just above the top of the specimen so as to give a value of the instantaneous velocity of the steel cylinder at impact. The distance between the wires was 40 ± 0.5 mm and the discrepancy between the counters was never more than 0.1 m/sec. Thus the velocity was known to within 3.25 per cent. This precision was sufficient with respect to the precision of the machining of the specimens. A very small lack of parallelism between the face of a specimen and that of the impacting hammer resulted in an oblique impact which required a much lower velocity to break the specimen. The experiments had a twofold purpose — (1) to observe the fracture pattern, and (2) to find relationships between the minimum velocity required to generate a fracture within a specimen and the

By H. l. Burghoff, J. S. Porter

This paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial Practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 90 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about Io per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrettl states the fiber axis of annealed 70-30 brass wire to be [111], with some indication of [IOO] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. Material and PRocedure All the wire for the investigation was processed from one portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02, nickel; 29.83 zinc (by difference). The billet section, 8 in, in diameter, was extruded hot to 3/4-in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 87s°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By H. l. Burghoff, J. S. Porter

This paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial Practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 90 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about Io per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrettl states the fiber axis of annealed 70-30 brass wire to be [111], with some indication of [IOO] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. Material and PRocedure All the wire for the investigation was processed from one portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02, nickel; 29.83 zinc (by difference). The billet section, 8 in, in diameter, was extruded hot to 3/4-in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 87s°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By W. T. Isbell

IN the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 14000 to 1500°F and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace was expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. EQUIPMENT AND ITS USES Dezincing Machine.-The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig I). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.-The treating cham¬ber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1947

By R. W. Raymond

CHARLES WILLIAM HENRY KIRCHHOFF was born March 28, 1853, at San Francisco, Cal., where his father, Charles Kirchhoff, was at that time employed in the consular service of his native country, Germany. A few years later, the family moved to Hoboken, N. J., in the public schools of which city the son received his preliminary education, proceeding later to Germany, where he was graduated in 1874 as mining engineer and metallurgist at the Prussian Royal Mining Academy of Clausthal, in the Harz. Upon his return to the United States, he became chemist of the Delaware Lead Refinery at Philadelphia, and retained that position for three years. But in 1877 he began what was to be an almost uninterrupted life-long association with David Williams, the publisher of The Iron Age, of New York, who established in that year, and continued for a brief period, a journal entitled the Metallurgical Review, on the editorial staff of which Mr. Kirchhoff received a place. The enterprise was doubtless an attempt to cover a wide metallurgical field outside of that which properly belonged to The Iron Age. But it was soon abandoned, and Mr. Williams wisely concentrated his energies upon the older journal, which, under his vigorous and skillful management, and the labors of the able editors and correspondents whom lie selected, became one of the greatest institutions off its class in the world. From 1878 to 1881, Mr. Kirchhoff was assistant editor of The Iron Age. From 1881 to 1884, he was managing editor of the Engineering and Mining Journal; in 1884 he returned to The Iron Age, to become for five years its associate editor, and in 1889, on the retirement of James C. Bayles, editor-in-chief. This list of dates and employments, without further comment, sufficiently indicates, at least to the eye of an expert, that Mr. Kirchhoff had found his congenial career in trade journalism. His qualifications for this profession were somewhat exceptional. He possessed the scientific training, the knowledge of foreign languages and literatures, and the power of making and keeping friends, which enabled him to get early notice of technical novelties; he had the taste for statistics which made him both industrious and intelligent in their collection and use; and to these traits he added a mastery of the meaning of such accumulated data, and a

Jan 10, 1916