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By Robert H. Aborn, J. J. B. Rutherford

It is now well known that troublesome intercrystalline corrosion may occur in austenitic stainless steels following exposure of the metal to a temperature within the range 1000° to 1500° F. (540° to 815° C.). The present paper describes a satisfactory method of estimating the extent of such corrosion, based on the measurement of the electrical resistance of a specimen before and after attack. This new method enabled us to study quantitatively the effect of several factors upon intergranular corrosion in the 18 Cr, 8 Ni type of alloy. The results show that susceptibility to this attack increases with increasing carbon content and grain size and appears to pass through a maximum for certain combinations of temperature of sensitization and period during which the alloy was maintained at that temperature; and are in complete accord with our interpretation of the mechanism of this phenomenon. The method is probably applicable to other metals or alloys subject to intercrystalline attack, such as the aluminum alloys of the duralumin type. The methods hitherto in use for estimating the degree of intergranular attack fall into three types: (1) microscopic examinationll (2) macroscopic examination of fractures, and (3) determination of the time required for complete failure or disintegration.2 None of these lends itself very well to a measurement of the extent of corrosion. The first two are qualitative in nature and the third provides an arbitrary value largely dependent on individual judgment, since failure is a progressive phenomenon and not a sudden event. Our experience is that weight-loss determinations, although valuable in some types of corrosion investigations, bear no simple relation to intercrystalline corrosion in this type of alloy, as is to be expected since the phenomenon probably involves only the thinnest films between adjacent metallic grains. Measurement of electrical resistance has been used recently in the study of some types of corrosion,3 but seems not to have been applied to

Jan 1, 1932

THAT the march of civilization has synchronized with progress in the art of utilizing minerals is a proposition that needs no proof. It is a truism. Historians conveniently divide the time that the earth has been inhabited into the Stone Age, the Bronze (more accurately the Copper) Age, and the Iron Age. As archeologists are not entirely in accord as to dates, and as a few centuries make no difference whatever to this particular story, it may be approximated that the Age of Copper began about 8000 years B.C. and that it gave place to the Age of Iron about 1000 years B.C. The logic of this succession-stone, copper, iron-lies in the fact that copper first displaced stone, then iron displaced copper as the standard material out of which the utensils, implements, and weapons, the utilitarian articles of antiquity, were made. After the advent of iron, the mining and smelting of copper continued. Copper and bronze found use particularly in objects of artistic and ornamental nature; but the superior qualities of iron for many purposes were recognized. Useful manufactures of those days consisted principally of knives, hammers, chisels, spear-heads, arrow-heads, and battle-axes. First these were made of stone, then of copper and bronze, then of iron-particularly as there was plenty of iron ore, and the metallurgy was comparatively easy of accomplishment. Of course, the periods of transition dragged slowly. Definite as were the three Ages dominated by the mineral substance from which they get their names, ten or fifteen centuries probably elapsed from the time the first iron was smelted in a small charcoal furnace until it became the accepted material from which to shape a battle-axe. Contrast this with the pace of modern progress. In a brief span, half a dozen more or less deserving candidates for the distinction of having their name

Jan 1, 1933

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,' will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

By Hugh S. Spence

The use of natural feldspathic rocks, as opposed to straight feldspar, for ceramic purposes is not new. "Cornwall stone," a semi-kaolinized granite containing fluorite, has long been used by the English pottery trade instead of feldspar, and "Carolina stone," a similar rock, is now being offered to the American trade. A recent report of the U. S. Bureau of Mines states that trachyte, a glassy volcanic rock, is being used in California instead of feldspar in ceramic bodies. In Germany, phonolite and basalt have been investigated, and possibly also used, as ceramic raw materials, and extensive research has been conducted in Russia in recent years looking to the utilization of the immense bodies of nepheline syenite of the Kola Peninsula, which is the host rock of the apatite deposits now being exploited on a large scale in the Murmansk region; the nepheline is recovered as a by-product of the concentration of the apatite. Long used principally as a raw material for the pottery and allied industries, where, in bodies, glazes, enamels, etc., it serves as a fluxing ingredient and forms, on firing, a glassy bond with the more refractory clay, flint and coloring particles, feldspar has been finding ever increasing employment in glass. In 1936, over half of the nearly quarter of a million tons of feldspar sold in the United States went to the glass trade. Its usefulness for this purpose is due to the resistance to thermal shock which it imparts to glass products, particularly bottles, containers and tableware, because of its alumina content, which averages from 16 to 20 per cent. Active search has been wade on the American continent during the past few years for other minerals of feldspathoid type, with comparable or higher alumina content, that, may be suitable for glass and other ceramic purposes. One of the most important results of this work has been the delimiting in central Ontario of large bodies of nepheline syenite of excellent, ceramic grade.

Jan 1, 1942

By Edward Keller

Someone some time ago remarked that some chemists still insist on telling us how to determine copper by the electrolytic method. The writer must confess that he believes that everything is not known definitely as yet as to how the exact amount of copper is determined in such material as purest commercial electrolytic copper. Some of us are not yet convinced that the pure copper atom is at all times deposited from an acid solution and that no oxygen or hydrogen will, under certain conditions, accompany it. Difficulties with impurer material are frequent, but erroneous results are not always apparent, since these do not speak so readily for themselves as those in the first case. By this is meant that if a chemist finds 100 per cent. of copper in electrolytic copper it is pretty certain that he perceives the result to be wrong, while if he finds 0.1 per cent. of copper too much in a very impure material he is far more likely to be unconscious of his error. These, in a wide experience, are frequent happenings and the writer has always looked with interest to publications on this subject. In turn, he feels justified in giving to others a few of his own observations. Up to a few years ago there were two methods of electrolytic copper assay in technical use, which had in common, that the amount of copper deposited on the cathode did not exceed 2 g., and they differed in that, for the one a large sample1 (20 to 80 g.) was taken from the general sample by a splitting device, dissolved, and from the solution a small portion (to contain 1 or 2 g. of copper) measured out for the electrolytic deposition; in the other method the copper was determined, generally in 1-g. portions of the separated coarse and fine portions of the sample, all of which passed a 16 or 20-mesh screen, being accomplished by a 40-mesh screen,

Jan 1, 1914

By Hugh S. Spence

The use of natural feldspathic rocks, as opposed to straight feldspar, for ceramic purposes is not new. "Cornwall stone," a semi-kaolinized granite containing fluorite, has long been used by the English pottery trade instead of feldspar, and "Carolina stone," a similar rock, is now being offered to the American trade. A recent report of the U. S. Bureau of Mines states that trachyte, a glassy volcanic rock, is being used in California instead of feldspar in ceramic bodies. In Germany, phonolite and basalt have been investigated, and possibly also used, as ceramic raw materials, and extensive research has been conducted in Russia in recent years looking to the utilization of the immense bodies of nepheline syenite of the Kola Peninsula, which is the host rock of the apatite deposits now being exploited on a large scale in the Murmansk region; the nepheline is recovered as a by-product of the concentration of the apatite. Long used principally as a raw material for the pottery and allied industries, where, in bodies, glazes, enamels, etc., it serves as a fluxing ingredient and forms, on firing, a glassy bond with the more refractory clay, flint and coloring particles, feldspar has been finding ever increasing employment in glass. In 1936, over half of the nearly quarter of a million tons of feldspar sold in the United States went to the glass trade. Its usefulness for this purpose is due to the resistance to thermal shock which it imparts to glass products, particularly bottles, containers and tableware, because of its alumina content, which averages from 16 to 20 per cent. Active search has been wade on the American continent during the past few years for other minerals of feldspathoid type, with comparable or higher alumina content, that, may be suitable for glass and other ceramic purposes. One of the most important results of this work has been the delimiting in central Ontario of large bodies of nepheline syenite of excellent, ceramic grade.

Jan 1, 1942

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The effects of increasing hydrogen content, introducing a notch, and changing the strain rate on properties of titanium and one of its alloys were investigated over a range of testing temperatures from —196° to 200°C. Both high purity and commercial purity A-55 titanium were used as representative a materials, while a commercial Ti-8 pct Mn alloy was used for an a-P alloy. It was found possible to analyze the data, using the ductile-to-brittle transition temperature concept. Increasing hydrogen, the presence of a notch, and increasing the testing speed raised the transition temperature for the a materials. The presence of hydrogen and notches raised the transition temperature of the a-B alloy also. However, increasing the testing speed generally decreased the transition temperature of the a-p alloy. IN previous papers, the authors have shown that hydrogen is most detrimental to the notch-bend impact toughness of a-titanium' and to the tensile ductility of a-B titanium alloys.' These general effects have been confirmed by Kessler and co-workers," and by Kotfila and Erbin." Kessler showed that the slower strain rate in notch-rupture tests was a more sensitive measure of hydrogen embrittle-ment of a-B alloys than the tensile test. In the present paper the authors cover, with tensile and notch-bend tests, the effect of testing speed, notches, and testing temperature on hydrogen em-brittlement. High purity and commercial purity titanium, examples of u materials, and a commercial a-,f3 Ti-8 pct Mn alloy were investigated. The purpose of the investigation was to correlate the factors producing embrittlement. Materials The high purity titanium for this investigation was obtained by arc-melting crystal bar from Foote Mineral Co. into 1 Ib ingots. As-cast hardnesses for these ingots ranged from 60 to 90 Brinell. The arc-melted ingots were forged to % in. diam rods at 1470°F. These rods were swaged to & in. diam at room temperature prior to machining of the specimens for hydrogenation and testing. The commercial A-55 titanium and the Ti-8 pct Mn alloy were obtained from Rem-Cru Titanium Inc., as % in. diam rod. The A-55 titanium was hot swaged to 1/4 in. diam at 1300°F prior to machining of the specimens for hydrogenation and testing. The a-p C-11OM alloy was hydrogenated prior to hot swaging to 1/4 in. roc1 at 1300°F. Hydrogenation prior to fabrication permitted testing of the a-P alloy in the equilibrated and stabilized condition. The equilibration and stabilization treatment used was an air anneal for 1 hr at 1300°F, followed by furnace cooling to 1100°F and then air cooling. Hydrogenation was done in a Sieverts apparatus described previously.' The hydrogenation treatment consisted of heating for 1/4 to 1/2 hr at 820 °C in purified hydrogen, slow cooling to 680"C, holding 1 hr for homogenization, and rapid cooling to room temperature. Intended hydrogen levels for the a-tita-nium materials were 0.05, 0.5, 1.0, 1.5, and 2.0 atomic pct—about 15 to 430 ppm. For the Ti-8 pct Mn alloy, the intended hydrogen levels were 0.05, 0.5, 1.0, 2.5, and 5.0 atomic pct—about 15 to 1100 ppm. The material for the 0.5 atomic pct level of hydrogen was vacuum annealed prior to hydrogenation to increase the accuracy of the addition. Vacuum annealing to remove hydrogen consisted of heating for 6 hr at 820°C, and resulted in a hydrogen content of about 10 to 15 ppm. When hydrogen contents were above 0.5 atomic pct—100 ppm—the hydrogen was added without prior vacuum annealing.

Jan 1, 1957

By R. F. Janke, J. F. Bossler

Introduction The commercial use of ion exchange resins to recover uranium evolved in the decade following 1950 when significant efforts were made to recover this vital element economically and efficiently from low grade ores. It was discovered that in both acid and alkaline systems, uranium exists as an anionic complex. This led to the application of anion exchange resins to concentrate and purify the uranium product. While this is the simplest statement of what an ion exchange resin does in the recovery of uranium, it should not be forgotten that the industry is continuing to evolve new methods in mining and processing which affect ion exchange operation. The inception of solution mining, the use of expanded bed ion exchange columns and the development of continuous ion exchange systems represent several examples of this continuing evolution in the industry. Throughout all of the changes in equipment designs and variations in solution compositions, the purpose of the ion exchange resin remains the same - to concentrate and purify uranium. Ion Exchange Resins When evaluating ion exchange resins for a uranium recovery project, the task that faces the chemist or process metallurgist is an assessment of the efficiency and, therefore, the economics of the various candidate resins for a given project. This assessment should include consideration of both physical factors such as particle size, density, hydraulic expansion and pressure drop as well as chemical factors such as the uranium loading and elution characteristics. For any given application, the differences in the physical and chemical behavior of ion exchange resins are a function of the conditions used to manufacture those resins. Therefore, an understanding of the way in which manufacturing variables affect resin behavior is important. Since most uranium recovery projects are concerned with recovery of the anionic complexes of uranium using anion exchange resins, this discussion will be restricted solely to the family of anion resins. The majority of the ion exchange resins used in commercial recovery operations look similar to the resins shown in Figure #1. [ ] Most of these materials are based on a styrene- divinylbenzene copolymer. The liquid monomers, styrene and divinylbenzene, are charged to a co-polymer reactor containing water. The water insoluble monomers are then mixed with the water to suspend oil-like droplets of the monomer mixture in. the water. The entire reaction mixture is then heated causing the monomers to polymerize into sol id thermoset plastic spheres. The spherical nature of the particle, the particle size distribution and the primary crosslinking level are fixed in this step in the production process. Figure 2 is a simplified illustration of this step of the process. [ ]

Jan 1, 1979

By R. V. Smith, E. J. Dewees, R. H. Williams

Before this paper was presented, the terms "f" and "v1/f in flow equations had been called "friction coefficient" and "friction factor," respectively. However, many authors have used the names for the terms interchangeably, with the result that considerable confusion has existed in the literature on flow of fluids. In an effort to establish a clear and concise terminology for these terms, the authors have designated f as "resistance coefficient" and dm as "transmission factor." Transmission factors for the flow strings of gas wells were determined by tests on wells in six fields of Oklahoma, Texas, and Louisiana. Data were collected on 14 gas wells while gas was flowing through 1 1/4, 2, 21/2, and 3-in. tubing and 51/2 and 7-in. casing. The transmission factors developed from these data were found to follow the resistance equation published by Nikuradse1 for turbulent flow in "rough" pipes with an average absolute roughness of 0.000,65 in. This average absolute roughness is believed to be representative generally of the flow strings of gas wells with the exception of those that have been exposed to corrosion or other conditions causing undue roughness. Also, use of an absolute roughness of 0.000,65 in. probably will result in transmission factors that are more representative of gas-well conditions than those in common use today, provided that the transmission factors are calculated by the methods outlined in this report. The authors believe that use of these transmission factors will permit calculation of more accurate subsurface pressures in gas wells than those in use today. Engineers use transmission factors in flow equations to compute subsurface pressures in flowing gas wells from measured wellhead pressures. These subsurface pressures are necessary for determining the productivity of gas wells from "back-pressure" tests. The methods of calculating pressures in flowing gas wells, as outlined by Rawlins and Schellhardt2 in Bureau of Mines Monograph 7, are based on the transmission factors in the well-known Weymouth formula" Natural gas engineers have realized that errors introduced by using transmission factors as given by the Weymouth formula are relatively unimportant in testing low-capacity gas wells; but they also know that such factors are important considerations in testing large-capacity wells. Accordingly, the research described in this report was undertaken to fulfill the need for more accurate means of calculating subsurface pressures in gas wells. This report is part of the Bureau's study of the flow of natural gas through pipe and commercial pipelines. Several of the conclusions regarding flow in the flow strings of gas wells were influenced by the results of the study of flow in horizontal pipelines. These instances are mentioned in the text of this report. METHODS OF COMPUTING TRANSMISSION FACTORS Methods and procedures for computing transmission factors for turbulent flow in circular pipes from test data taken on gas wells have been derived and explained in detail in a paper by Smith4. As these methods were used to calculate the transmission factors presented in this report, a summary is included. Starting with

Jan 1, 1955

By W. F. Carew, H. D. Kessler, F. A. Crossley

AS part of a program on phase relationships and transformation processes of titanium alloy systems, the titanium-rich corner of the Ti-Mo-V system has been investigated. This region was surveyed primarily to supply information toward the development of a creep resistant, weldable alloy, with a minimum alloy content, for use in the 425° to 550 °C range. Specifically, the investigation was directed toward the development of a stable ß alloy with less total alloying additions than is found in the Ti-30 pet Mo alloy. A secondary objective was the development of a creep resistant, weldable a-ß alloy for application around 300°C. Molybdenum was selected as primary additive to titanium on the basis of an investigation1 which showed that the Ti-30 pet Mo alloy had promising elevated temperature tensile properties. Furthermore, aging studies1 showed no tendency for this

Jan 1, 1957

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,&apos; and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.&apos; Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

Discussion of the paper of O. P. Hood, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2607 to 2611. R. V. Norris, Wilkes-Barre, Pa.-I have had a little experience with gasoline locomotives and I want to indorse very strongly Mr. Hood&apos;s point with regard to the danger of carbon monoxide poisoning. I think .the terrible danger is not fully realized. I was foolish enough some time ago, in investigating a gasoline locomotive, to attempt to walk out of the mine entry behind it, and for several days I felt very seriously the carbon monoxide effects. The use of gasoline locomotives ought to be confined to mine entries where there is a very large amount of air. One of the grave dangers is their great convenience and the temptation to run them into chambers for just a few moments to get a car or two. GEORGE S. RICE, Pittsburgh, Pa.-Apparently one of the great dangers is in the style of the gasoline engine. When my attention was. first directed to the type of gasoline locomotives which I saw in the foreign mines-France, Belgium, and Germany, I was most favorably impressed with them, and they have given no trouble on account of fumes, so far as I could learn. Large numbers of them were being used, but all were of small capacity, and of a kind in which the speed control is by a governor of the hit-or-miss type, the engine running continuously. Their power capacity was very low, if I remember correctly it was not over 4 or 5 h.p., but they were used under favorable conditions where the grades in the mines were slight, since the entries or tunnels bad a slight grade in favor of-the load, making about the same pull for the empties against the grade as for the load with the grade. I understand the hit-or-miss valve arrangement enables a setting that will give more perfect combustion than can be insured with the valve controlled by the operating man, as in the automobile type of valve and engine used in this country. Apparently the European type of locomotive does not have the capacity to permit use under the conditions existing in this country, where most of our entries or tunnels have variable grades and long heavy trips of mine cars are used.

Jan 4, 1915

By Earl Bardwell

THE structural relations existing between cuprous oxide and copper -were first systematically studied by Heyn1&apos;, who suggested that a study of the microstructure of refined copper might be substituted for the analytical methods in vogue for determining the oxygen content of copper coming from the refining furnace. Hofman, Green and Yerxa,2 in their paper A Laboratory Study of the Stages in the Refining of Copper, working along the lines suggested by Heyn, showed that a study of the microstructure could be made to yield a correct estimate of the oxygen content of the specimen of refined copper under examination. In order to determine the oxygen content of the specimen of refined copper under. examination a photomicrograph was first made. From the relative areas of copper and eutectic, the percentage of cuprous oxide and the corresponding percentage of oxygen were then readily calculated. It was found that the values for oxygen thus obtained corresponded closely with the analytical results. With the idea of utilizing this method of determining the oxygen content of each charge dipped from the refining furnaces at the Boston & Montana Reduction Plant, the physical testing laboratory was equipped with suitable apparatus for carrying out the work. It may be of interest to describe certain of the methods which have been worked out in this connection and give such data as have been obtained bearing on the effect of the oxygen content of refined copper upon its conductivity. Apparatus.-For the benefit of those who may be unfamiliar with metallographical apparatus and methods and may be interested to know what equipment is required, a few words with regard to the apparatus is in place at this point.

Jan 7, 1913

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By Wheeler Davey

WHEN metals are subjected to mechanical working, such as rolling, one of the phenomena that take place is a movement of the crystals of the metal into a system or systems of orientation which bear an angular relation to the direction of working. In rolled metal the crystals may orient themselves with respect to the rolling plane or the rolling direction, or both. Direct evidence of the existence of preferred orientations in rolled metal has been obtained by numerous investigators from X-ray patterns of the rolled metal. Most of these workers used a monochromatic pinhole method. Where the degree of preference for a single orientation is high the monochromatic pinhole pattern may be interpreted by a geometrical calculation based on the angular relationships of the planes in the crystal and the diffraction arcs on the X-ray pattern. This process may be aided by the geometrical construction of the locus sphere (Langenkugel), and reflection circles of Polanyi,1 Polanyi and Weissenberg,2 and Mark and Weissenberg,3 and of the plane polar figures (flachenpolfigur) of Franz Wever.4 R. M. Bozorth5 solves X-ray patterns from metals having a single preferred orientation by means of a series of charts which when placed over the X-ray pattern give directly certain angular relationships, between the crystal planes and the surface of the specimen.

Jan 1, 1929

By Clair Upthegrove, Elbert S. Rowland

THE widespread interest in the alloys of beryllium with copper is due principally to the fact that certain compositions show very favorable precipitation-hardening characteristics and are, in fact, the strongest nonferrous alloys known at the present time. Investigations have been conducted by Masing and Dahl and others on the physical characteristics of ternary beryllium alloys, in an attempt to produce precipitation-hardening effects with a smaller amount of beryllium than that required in the binary copper-beryllium alloys (2.0 to 2.5 per cent Be). The results of these investigations show that ternary alloys of beryllium with Cu-Sn, Cu-Al and Cu-Zn, among others, exhibit promising improvements in physical properties after precipitation-hardening treatment and, while the increases in properties obtained are not as high as those realized from the binary copper-beryllium alloys, excellent properties are: obtained with beryllium contents averaging about one-half the amount required in the binary alloys. This paper presents the results of an investigation of the equilibrium relations of certain alloys containing copper, tin and beryllium. The alpha-phase boundary of the ternary system is given for alloys containing from. 0 to 1 per cent beryllium. The equilibrium conditions beyond the alpha-phase boundary are presented for alloys containing up to 32 per cent tin and 1 per cent beryllium. The data were collected by means of

Jan 1, 1935

By Alfred H. Bell

The year 1937 has been outstanding in the history of the Illinois oil industry. During the course of the year the state&apos;s daily production has been trebled, increasing from 12,000 bbl. per day at the beginning to 37,000 bbl. per day at the end, and the year&apos;s total, 7,426,000 bbl. is 66 per cent above the previous year&apos;s production of 4,475,000 bbl. The production in January was 368,000 bbl.; in December it was 1,085,000. Production from the old fields increased slightly. Most of the new production is from fields in the central part of the Illinois Basin, an area that for many years was considered unfavorable to the occurrence of oil and gas. The principal producing horizon of the new fields is the McClosky "sand," an oolitic limestone in the Ste. Genevieve formation of lower Mississippian age. Although development has not yet gone far enough to permit accurate estimates of oil reserves in the new fields, it is believed that they are of the order of 100,000,000 barrels. The following are the oil fields discovered in 1937 listed in order of amount of daily production at the end of the year; Noble (Richland County), Clay City, including Southeast Clay City (Clay and Wayne counties), Patoka (Marion County), New Centralia (Clinton County), Olney (Richland County), Cisne (Wayne County),.Beecher City (Fayette County), and Rinard (Wayne County). One gas field, the Russellville, in Lawrence County, was discovered in 1937. For locations of the new fields see Fig. 1. A generalized geologic column for Illinois, showing producing horizons in the new fields, is given in Fig. 2. The total productive area of the new fields at the end of 1937 was 1712 acres, in which 230 wells were producing. Thisrty-five dry holes were drilled within 1/4 mile of producing wells. At the end of the year there were 19 drilling wells, 28 rigs standing, 18 rigging up and 4 new locations in these fields. In the whole state 447 wells were completed, of which 284 were oil producers and three gas producers. Total initial daily production of

Jan 1, 1938

By G. Y. Chin, M. T. Dolan, W. L. Mammel

The least work analysis of constrained deformation, first proposed by Taylor and recently modified by Chin, Hosford, and Mendorf to include twinning, has been applied to the problem of axisynmetric flow. Calculations were made, for the case of (111}(110) slip and {111}(112) twinning applicable to fcc deformation. The solutions were obtained by linear programming techniques and with the aid of computer methods. The results show that in axisymnzetric tension the onset of twinning tends to decrease the plastic strength anisotropy as compared with the case of defortnation by slip alone. In compression, however, the strength anisotropy is increased as a result of twinning. The [100] and 11111 orientations and their vicinity are unfavorable for twinning in tension and compression, respecticely. With slight modifications, the present results may be applied to bcc metals deform ing by {110}(111j slip and (112} (111) twinning. Implications of present results to wire texture development of low stacking fault energy fcc materials arc discussed. PREVIOUSLY we&apos; have applied linear programming techniques to obtain solutions to Taylor&apos;s least work analysis2 of constrained deformation of single crystals undergoing axisymmetric flow, such as occurs in an axially loaded polycrystalline aggregate. These solutions yielded values of the parameter M = o/.r = Y/w which relates the external stress-strain (u-c) curve to the shear stress-shear strain (7-y) curve for the crystal. The value of M is dependent on crystal orientation and hence enters significantly in texture strengthening considerations.3&apos;4 Recently the Taylor hypothesis was modified by Chin, Hosford, and Mendorf&apos; to include mechanical twinning. The latter has now been applied to the problem of axisymmetric flow and the results are reported in this paper. Calculations have been made for {111 )( 110) slip and {111 )(112) twinning applicable to fcc crystals. With minor changes in the indices of the slip and twin systems, the present results are also applicable to bcc crystals which slip on (110) (111) and twin on {112)(111) systems.

Jan 1, 1970

By W. C. Coffin

Fire-brick stoves have become a necessary part of the modern coke blast-furnace equipment, and are also superseding the cast-iron pipe stoves in anthracite- and charcoal-furnaces. The brick stoves in general use are of either the Cowper or Whitwell type, or modifications of these bearing the names of those who invented the alterations from the original types rather than any real departure from then]. All these stoves have approximately the same valve-equipment and follow the same line of operation. The waste gas from the furnace enters at one port and burns in a single combustion-chamber, and the heated products are drawn through the various passe; in the brickwork to a stack of proper height to create the necessary draught. The last passes of these stoves receive a very small percentage of the heat from the gas, owing to their extreme distance from the combustion-chamber; and this chamber also suffers great deterioration in the attempt to force the heat into the farthest passes. At best, about 70 per cent. of the heat taken up is held in the combustion-chamher and the first down-pass of the Whitwell stoves. Mr. Hugh Kennedy, Manager of the Isabella Furnaces, Pittsburgh, Pa., who has had a large experience with the fire-brick hotblast stoves, was so strongly impressed with the fact that but about thirty per cent of the brick of the average stove were doing proper duty as heat-agents, that, after careful study and experiment, he had three 20- by 60-feet stoves constructed with a view of more uniformly heating all the brick. In these the general lines of the Whitwell stove are followed, with the blast-connections unaltered, but gas is introduced at the bottom of each pass, and outlets are provided at the top, so that the gases have a direct natural draught in each pass and the highest heats are obtained at the bottom instead of the top. The natural tendency being toward the reverse condition, the brickwork soon acquires an almost uniform temperature.

Jan 1, 1893