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By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

Experimental work on the properties of high-purity alloys of the copper-man-ganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. Previous Work Heuslerl conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilib- rium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alpha-beta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350' to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur6 have also noted this precipitate. Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By C. M. Brown

Selection criteria for the instrumentation employed in semi-autogenous grinding circuits are reviewed. Instruments in use for grinding mill and related process equipment start- up, shutdown, protection, monitoring, control, and performance reporting functions are discussed with examples given of current industry practice. The quantity and type of instrumentation used vary from operation to operation, but today many semi- autogenous circuits are highly instrumentated, and employ automatic process control for both circuit stabilization and optimization of economic performance. Examples of analog and digital based control systems exist, and are described.

Jan 1, 1982

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By Chung Yu Wang, Guy C. Riddle

There are found in nature upward of II2 minerals containing antimony, but only a few of them, listed in Table I, can be considered as antimony ore-forming minerals. Stibnite (Sb2S3), antimony sulphide or glance, is the principal ore of antimony. The oxide ores—cervantite, kermesite, valentinite, sernarmontite—occur sparingly in nature. Dry methods are generally adopted for the extraction of the metal. Electrometal-lurgical methods have had much attention in America and Germany and have not yet found, on economic grounds, practical or extended application, except in a few places. During recent years, treatment of the poor grades of the ore, especially sulphide, by ore-dressing methods, has commanded some attention and been adopted at a few plants. The impure sulphide of antimony, resulting from the liquation process, is called lLneedle," "liquated" or "crude" anti- mony, and the refined metal itself is called antimony "regulus." The different processes for the treatment of antimony ores are shown in the diagram of Fig. I. Liquation of Crude Antimony The first step in the smelting of antimony is a simple one, the process of LLliquation," which produces crude or needle antimony. Ores containing $ 50 per cent Sb are used in the liquation process for the production of crude. The temperature required for liquation is between 550' and 600°C. Ores to be liquated are broken to about walnut size. If the pieces are larger than this, the low heat used will not penetrate' effectively, and if they are smaller the ore tends to pack too closely for adequate penetration. A packed charge also prevents the free escape of the fused sulphide. Intermittent Liquation in Crucibles The unique type of furnace that is in use in China for smelting is not highly efficient but is simple in construction and operation. The furnace is generally built

Jan 1, 1944

By J. A. Herrick

FOR a long time, especially in Europe, heavy pieces of forgings, such as cannon, armor plates, marine shafting, etc., have been steadily augmented in size, more particularly since steel has been substituted for wrought iron. To keep pace with these forgings several, very large hammers have been, from time to time, erected. The most powerful and thoroughly appointed of all now in operation is that designed and built by Messrs. Schneider & Co. at their works at Creusot, and it is the design of this communication to give to the members of the Institute a concise description of this remarkable piece of mechanism, which I have taken from an article published in the Annales Industrielles. This hammer is rated nominally at 80-tons power, but its capacity is, in reality, far greater, as will be seen by the comparative figures given later. The complete plant, comprising the hammer, the cranes, the furnaces, and the building which shelters the whole, is distin-

Jan 1, 1880

By A. Matsubara

Jan 1, 1922

By A. Matsubara

Jan 1, 1922

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.'-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23'24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300' and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By J. A. Herrick

For a long time, especially in Europe, heavy pieces of forging, such as cannon, armor plates, marine shafting, etc., have been steadily augmented in size, more particularly since steel has been substituted for wrought iron. To keep pace with these forgings several very large hammers have been, from time to time, erected. The most powerful and thoroughly appointed of all now in operation is that designed and built by Messrs. Schneider & Co. at their' works at Creusot, and it is the design of this communication to give to the members of the Institute a concise description of this remarkable piece of mechanism, which I have taken from an article published in the Annales Industrielles. This hammer is rated nominally at 80-tons power, but its capacity is, in reality, far greater, as will be seen by the comparative figures given later. The complete plant, comprising the hammer, the cranes, the furnaces, and the building which shelters the whole, is distin-

Jan 1, 1880

Jan 1, 1957

By John N. Dew, William L. Martin, `

This paper describes the results of a laboratory investigation conducted to obtain data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. Air and fuel requirements, rates of advance, com-bustion temperatures, and coke and fluid distributions are presented. The mechanism of oil recovery by in stiu combustion is discussed. Five crude oils ranging in gravity from 10.9 to 34.2"' API were prodrrced from a semiadiabatic, uncon-.solidnted sand pack by in situ combustion. Experimental conditions were varied over a wide range in order to determine the inter-relation-.ships of process variables. The mini-mum air flux requirement for self-sustained combustion was found to he less than 10 scf/hr-ft'l. The rate of advance of a self-sustained combustion zone was found to be nearly proportional to the air flux at the combustion front. The effects of presrure and injected air flux were studied in a series of experiments using a 21.2" API crude. A minimum air require-ment was observed at an air .flux of 20 scf/hr-ft'. The oil saturation con-sumed as fuel averaged 5.5 per cent of pore volume. The effect of air pressure was, found to be .small for experiments having high combustion eficiencies. This study should promote a better understanding of the problems and mechanisms involved in labora-tory investigations and field applications of the in situ combustion pro-cess. The data presented will be use- ful in the interpretation of results of field tests. When tempered with volu-metric sweep efficiencies, the data can be used in making preliminary economic appraisals of the process as applied to reservoirs containing high porosity unconsolidated media. INTRODUCTION The purpose of this work was to obtain laboratory data for an evaluation of the in situ combustion process as a method of producing crude oil from reservoirs. In situ combustion basically consists of (1) injecting air into a reservoir through selected input wells to create an air sweep through the reservoir, (2) igniting the crude at the injection well, and (3) propagating the combustion front through the reservoir by continued air injection. By this means, oil is swept toward producing wells in the area. The fuel for combustion is supplied by heavy residual material (coke) which has been deposited on the sand grains during distillation and cracking of the crude oil ahead of the combustion front. Recovery of petroleum by a combustion or heat wave process is not a new idea. F. A. Howard was granted a patent in 1923 on a process in which air and a combustible gas were pumped into an injection well and ignited.' Russian engineers reported on field experiments with a crude oil gasification process in 1935'. Other known early field tests include those conducted near Bar-tlesville and Ardmore, Okla., in 1942." More recently completed field tests include an inverted seven-spot by Sinclair Oil Co. in the Delaware-Childers field, Nowata County, Okla.'; a three-well and an inverted five-spot test by Magnolia Petroleum Co. in Jefferson County, Okla."."; and a test by California Research Corp. in the Irvine-Furnace field in Kentucky. The Worthington Corp. has completed a test in cooperation with the Forest Oil Corp. in Clark County, 111.l Several field tests are now in progress. Sinclair has acquired a 600-acre lease in the Humboldt-Chanute field, Allen County, Kans., and is under way with a large-scale operation. Three field tests are under way in California. The General Petroleum Corp. is conducting an inverted five-spot pattern test in the South Bel-ridge field in Kern County under a cooperative agreement with 11 other companies, including Continental Oil Co. California Research Corp. is conducting a four-well pattern test in Midway-Sunset field near Maricopa, and Richfield Oil Corp. is under way with a test in the Ojai field in Ventura County. Although the published information is valuable concerning results of field tests, little laboratory data other than that reported by Kuhn and Koch5 are available to aid in appraising the tests from a technical or economic standpoint. Engineering data needed to evaluate the process include the amount of air required per barrel of oil recovered, minimum injection rates which will support combustion, rates of advance, air required per unit volume of reservoir cleaned, amount of oil recovered, and amount of oil consumed as fuel. The present laboratory investigation was undertaken to provide these data for that portion of the reservoir swept by the combustion zone. The first phase of this investigation was exploratory in nature and was conducted at injection pressures less than 100 psig. Data were ob-

By W. C. Ellis

NONFERROUS alloys upon which desirable properties can be conferred by heat treatment are becoming of increasing industrial importance. The alloys of copper with a constituent which has a solubility varying with temperature are materials of this character. Some of the constituents which are effective in producing a change in the mechanical properties of these alloys upon heat treatment are, according to Corson,1 nickel and silicon, iron and silicon, cobalt and silicon, and chromium and silicon. In addition to these elements, Gregg2 states that the combination of beryllium and silicon is effective in producing age-hardening characteristics in copper. The effect of these elements, however, as dispersion-hardening constituents in the copper alpha solid solutions does not seem to have been studied in any considerable detail. This paper deals with the heat treatment and properties of three alpha brasses containing 3 per cent. of nickel plus silicon in the proportion necessary to form the compound nickel silicide, Ni2Si. Some information of a preliminary nature in regard to the hardening by heat treatment of phosphor bronze containing the same percentages of nickel and silicon is included. The method of hardening the alloys, which is effective in increasing the tensile strength and proportional limit, is similar to that used in, the case of duralumin type aluminum alloys. It consists of a quench from a temperature at which the hardening constituent is in solid solution, followed by an aging at a lower temperature to precipitate the dissolved constituent in a dispersed condition. This results in an increased resistance of the alloy to deformation with an attendant improvement in the tensile properties.

Jan 1, 1929

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

A. Blainey (Ministry of Supply, Atomic Energy Research Establishment. Hnrtoell. England)—With ref- erence to the published work of Hausner et al. on the powder metallurgy of zirconium, it will be of interest to summarize briefly the results of preliminary work we have carried out on this subject at A.E.R.E., Harwell. For the early experiments we used zirconium

Jan 1, 1953

By D. A. Belforti, M. P. Lepie

Spectroscopically pure copper was melted on sapphire plaques in a zydrogen atmosphere. The surface tension of the liquid metal was determined using the sessile drop technique. Measurements were made by direct observation with the aid of a specially const,mcted telescope. The value obtained, 1268 dynes per cm, is compared to that found in the literature. THERE is at this time considerable interest in the use of ceramics for vacuum tubes. The crystalline material is superior to the more conventional glass in mechanical strength, chemical inertness, dielectric properties, ability to withstand high temperatures, and so forth. However, ceramics are much more difficult to seal hermetically with metals than are the glasses. For this reason an investigation was undertaken to determine the wetting and adhesion of metals to ceramics. The sessile drop technique offers a convenient means at elevated temperatures for measuring liquid surface tension, wetting angle, density, spread- ing coefficient, and work of adhesion. Thus, from the contour of a drop of liquid at rest on a solid surface one can obtain a quantitative evaluation of the degree to which the two substances will bond. To this end a special apparatus was constructed so that various molten metals could be observed. Standardization of the apparatus was done initially by measuring the surface tension of copper since this is well documented in the metallurgy literature. Although there are many methods available for the measurement of surface energy,'+ the sessile drop technique has been used most extensively for molten metals and ceramics.5"' Fig. 1 illustrates the dimensions to be measured. From these values, the surface tension of the liquid can be obtained using the Bashforth and bdams' equation and tables.

Jan 1, 1963

By AIME AIME

T HE Mining Methods Committee held its initial meeting* on Tuesday afternoon, with F. W. Bradley in the chair and W. Y. Westervelt as vice- chairman. The first paper to be presented was "A Plea for a U. S. Court of Patent Appeals," for which Kenneth W. Greenawalt ably pleaded. The paper (which was published in full in last month's issue) is so carefully prepared that no synopsis can do it justice. It discusses the opposed views of some patent lawyers and other lawyers and members of the judiciary as, for example, Chief Justice Taft who is quoted as saying in 1921: "I think it is a great deal better to take a first class lawyer and a first-class judge and make him a good patent expert than it is to take a patent expert and try to make him a first-class lawyer and a good judge." Mr. Greenawalt argued the need for specialized scientific and engineering interest and understanding to enable a lawyer or judge to prepare or interpret patent specifications and decide the originality necessary for a valid invention. He proposed the special U. S. Court of Patent Appeals to also counteract the costly confusion and injustice now ruling where a patent may be declared valid in the courts of certain States and invalid by the courts of other States.

Jan 1, 1930

New Products Equipment

Jan 6, 1953

By J. L. Bray

LEAD has often been suggested as a protective coating for iron and steel. Such a protective coating should possess: (1) good adhesion, (2) durability, (3) ease of application, (4) freedom from pinholes, (5) good appearance and (6) low cost, but, unfortunately, lead coatings so far produced do not have all of these characteristics. Because of the necessity of carrying out the coating process cheaply, and because lead solutions have poor plating characteristics, most of the efforts have been directed toward the hot-dipping process rather than electroplating. The hot-clipping processes using lead have not been successful chiefly because of the lack of adherence between iron and lead. In any coating process involving iron a bond can be obtained only by the formation of an intermetallic compound, the formation of a solid solution, or mechanical means. Lead forms with iron two immiscible liquid solu-tions, and in the solid state no intermetallic compounds or solutions. It is necessary, therefore, to employ some other element or elements as a binding agent. Tin may be used as in terneplate, or copper in the form of a thin film of electrolytically deposited metal to which the lead will adhere. Because of its physical and chemical properties, lead as a coating medium would undoubtedly be limited in its use to sheet and wire and then only when the article is not subject to abrasion or wear. A very large tonnage of these products are being used under such conditions and a successful lead-coating process should be a valuable contribution to the science. Two other difficulties stand in the way of successful lead coating-that of poor appearance of the weathered surface and the tendency of the lead to form pinholes during solidification. Since lead is commonly accepted as cathodic to iron, these exposed areas are ones of accelerated corrosion.

Jan 1, 1937

Charles H. Morgan, Worcester, Mass. (communication to the Secretary): In connection with Mr. Douglas's mention of the continuous charcoal kiln used at Kopparberg, some further data concerning this important invention may be of interest. Before giving these, however, I will say a word or two concerning other features of Swedish practice. In 1894 I spent two days at Soderfers with Mr. Tom Bergendal, the manager of the works, and was specially interested in the gas-producers and wood-drying kiln, illustrated in the paper contributed to our Transactions by Mr. Odelstjerna in that year.* The wood-drying kiln is, however, quite different in design and construction from Ljungberg's charcoal kiln. In the summer of 1894 it was discovered that by placing the gas-producer as close as possible to the open-hearth furnace, and working the producer hot, ordinary weather-dried wood, still containing a considerable percentage of moisture, could be used to advantage in the melting-furnace. Hence, the dryingkiln was needed for wet wood only. One of the iron-works of the Udeholm Go. was the first to adopt the Lundin saw-dust gas-producer and condenser, enabling them to make gas from saw-dust containing 45 per cent. of moisture, and convey the gas from the condenser through wooden pipes to the Siemens steel-melting furnace.† This sawdust gas gave very satisfactory results in iron-works; but the proprietors experienced much trouble by reason of the pollution of rivers by the tar-water from the condenser. On my visit, in 1894,I found that the Udeholm Co. had put in for their steel-melting furnaces the same wood-gas producers

Jan 1, 1899

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963