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By D. O. Noel, E. B. Gebert, J. D. Shaw

It is, of course, expected that manufacture of the various metal powders should involve numerous methods adapted to the specific characteristics of the metals themselves. Several methods for powdering a particular metal may be available, but the physical characteristics of the powder as produced by the several methods may be quite different. In the final analysis, the application of the metal powder dictates the physical properties that the metal powder must possess, and this, to a very large extent, will determine which of several possible methods of manufacture is adopted. Sometimes powder of the same metal is produced by more than one method, each powder having specific characteristics that make it particularly suitable for its application. For purposes of classification, the various methods of powdering metals can be grouped as follows: 1. Machining. 2. Milling (by ball mills, stamps, attrition mills, etc.). 3. Shotting (pouring molten metal into water, air, etc.). 4. Granulation (by stirring molten metal while solidifying). 5. Atomizing (disintegrating by steam, compressed air, etc.). 6. Condensation of metal vapor. 7. Reduction of oxide powders. 8. Chemical precipitation. 9. Electrolytic deposition. 10. Sintering (for producing alloy powders). 11. Formation of an alloy followed by dissolving or otherwise removing one of the alloying constituents. Machining Turnings, cuttings, filings, etc., are, of course, produced as by-products in machine work of various kinds, and find certain applications as metal powders. For example, iron powder so produced is used extensively as a reducing or precipitating agent and as a constituent in certain hard-finish cements.

Jan 1, 1938

By T. D. Yensen, R. K. McGeary

While we have not been primarily interested in the determination of hydrogen in the alloys that we have been dealing with, we arc very glad to cooperate in this symposium on sampling and analysis for hydrogen, as we can never tell when we may find it desirable to perform such analyses. Vacuum-fusion Method Our primary interest has been oxygen and carbon, in the analysis of which we think we have become very proficient. Our oxygen-analyzing apparatus is of the vacuum-fusion type (Fig. I). This employs Dr. Derge's type of graphite cruciblc and slit sleeve, with graphite powder between, for heat insulation (Fig. 2) supported in a clear quartz bulb connected to the Pyrex glass system by means of a carefully made ground joint. The latter is kept cool by means of an air blast from a circular copper tube surrounding the joint. The crucible is heated by high-frequency induction and the 24 one-gram samples successively dropped in from the horizontal tube at the top by means of a magnet. The gases (H², CO, N2) are passed through the CuO catalyst held at 300°C. (converting CO to CO²I, H² to H²O) and the CO² and H2O frozen out in the main liquid air trap, while N2 is evacuated. At the end of the operation, shown by the termocouple vacuum gauge indicating a pressure of 10-4 mm. Hg, the analyzing system is isolated by means of the mercury cutoffs, and the CO² and H2oare determined by transferring first the CO2 and then the HzO to the small trap at the right. This is done by placing liquid air on the small trap, then removing the liquid air from the large trap for one minute, which is sufficient to evaporate the Co2 and transfer it to the small trap. The CO2 is then measured by closing the mercury cutoff at the extreme right, removing the liquid air from the small trap, warming it up to room temperature, adjusting the mercury level to one of the three marks on the glass tube (corresponding to three volumes calibrated so that I mm. Hg of CO² corresponds to 0.001, 0.002 and 0.010 mg., respectively, of oxygen) and finally reading the pressure. Liquid air is now replaced on the large trap, the mercury cutoff at the right opened, transferring the COz back to the large trap. The cutoff to the pumps is then opened, the liquid air removed for one minute, thus evacuating the CO², the pumps again cut off and the H2 O transferred to the small trap as before, except that it is now necessary to warm the large trap with a Bunsen burner in order to evaporate all the H2O. This requires about three minutes, as the inner tube must be heated to at least 100°C. In order to prevent H²O from being adsorbed on the glass walls, the glass tubing beyond the catalyst (i.e., to the right in Figs. I and 3) is kept heated to about 150°C. by means of Nichrome ribbon as shown in Fig. 3. For a I-gram sample the above amounts of oxygen (0.001, 0.002 and 0.010 mg.) 35

Jan 1, 1945

By Earl Ingerson

BORE surfaces of used guns commonly show a pattern of cracks in various degrees of development. It has been suggested that these cracks may aid erosion by providing channelways for the gases, eventually leading to the tearing out of blocks of metal. Under the general studies of gun erosion conducted at the Geophysical Laboratory it appeared desirable to consider this factor, and to determine the resistance to surface cracking offered by gun steel and by various other materials that might be used in the bores of guns. METHOD AND APPARATUS In order to make such a determination it is necessary to have (I) an arrangement in which the surface to be studied can be subjected to conditions similar to those in a gun with respect to temperature, pressure (developed by explosion gases), composition of the gases and length of time the surface is exposed to the gases; and (2) a specimen that can be examined readily after any number of shots, and then fired again, if necessary. The first of these conditions can be met by using an explosion vessel designed by H. S. Roberts of the Geophysical Laboratory. Fig I shows a cross section of the apparatus. The "gun" G from which the charge is fired is made from the receiver of a caliber 0.30 army rifle, M1903, and the charges are prepared in caliber 0.30 cartridge cases. The test specimen S is held in place by a cone-shaped plug P and by a steel ,bridge B which is bolted to the outside of the explosion vessel on either side of the section shown. The plug, in turn, is held in place by a screw collar C. Maximum pressure is controlled by a brass rupture disk R. Part of the explosion gases flow past the two flat areas on S. st the two flat areas on S. Temperature and composition of gases, and the time before the rupture disk breaks, can be controlled by amount and kind of powder used, and pressure can be controlled by using rupture disks of different thickness. While the explosion vessel used was not designed so that temperature and pressure could be measured, in other vessels of closely similar size and shape containing proportionate charges of the same kind of powder as that used for standard testing procedure, values of 2700°K and 5000 psi were obtained. Since the orifices past the flat areas on the plug are small compared to the rupture disk hole (1:16), most of the gas goes out through the rupture disk when it breaks. The amount that goes by the plug depends on (I) the pressure attained before the rupture disk breaks and (2) the time it takes for this pressure to be built UP. The second condition (examination at will after any firing) is met by using for specimens short rods that have flat areas ground on opposite sides. These flat

Jan 1, 1947

By J. H. Richards, G. Derge, W. Peifer

A WIDE Variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware, They have been related to hydrogen largely by circumstantiat evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British committee on the Heterogeneity of Steel Ingots,' and current approaches to the problem were reviewed in a recent symposium of the AIME.I2 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principal object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem, The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow in However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross-section large enough to develop cracks, Yet small enough for convenient handling and sampling. Rails were also selected because they arc made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitat~s early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion, (2) Vacuum extraction (without melting), (3) Total combustion.

Jan 1, 1949

By G. Derge, W. Peifer, J. H. Richards

A WIDE Variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware, They have been related to hydrogen largely by circumstantiat evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British committee on the Heterogeneity of Steel Ingots,' and current approaches to the problem were reviewed in a recent symposium of the AIME.I2 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principal object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem, The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow in However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross-section large enough to develop cracks, Yet small enough for convenient handling and sampling. Rails were also selected because they arc made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitat~s early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion, (2) Vacuum extraction (without melting), (3) Total combustion.

Jan 1, 1949

By Charles G. Maier

It has long been supposed that when crystalline materials are comminuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1.t The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chemical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the corrected heat of solution was less for fine material than for coarse. Continuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. Similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by Rosenhain and Stott4 and by Taylor and Quinney9 The results obtained by the different investigators were not satisfactorily consistent, but the experiments of Taylor and Quinney constitute by far the best figures obtained to date. The previous paper1 presented evidence to show that if energy is stored in the surfaces of crystals the densities of fine crystals should differ

Jan 1, 1936

By H. A. Bedworth, W. H. Bassett

The amount of oxygen present in refined copper bears an important relation to the effects of various impurities on physical properties of copper, as well as the effects of reducing gases at higher temperatures. It seems fitting at this time, when the effects of reducing gases on copper are being discussed, to describe methods that have proved satisfactory for the determination of oxygen and sulfur, and to present some results obtained by investigation of these methods in the authors' laboratory. The procedure for the determination of sulfur is closely interrelated with that for oxygen and has, therefore, been included. It was first proposed by Hampe1 that oxides in copper could be accurately determined by the loss in weight sustained by finely divided copper when reduced at red heat in pure hydrogen, or by the weight of water produced. Hampe's method was later modified by Archbutt,2 who established the accuracy of the method and demonstrated that equally accurate results were obtained by noting the loss in weight or by weighing the water formed. The determination of oxygen by heating in carbon monoxide has been proposed by West.3 In our hands this method has given slightly lower results than obtained by heating in hydrogen. Heath4 found that the loss in weight after heating in hydrogen did not represent the true oxygen as cuprous oxide but included also gases derived by the metal from the fuel and refining in the furnace, and any trace of mechanically held moisture. He found, further, that the copper after ignition retained hydrogen equivalent to about 0.01 per cent. Heath proposed to determine the amount of occluded gases by preliminary ignition for 20 min. in pure carbon dioxide—and to correct the error caused by absorbed hydrogen by subsequent ignition and cooling in carbon dioxide, finally replacing this gas with air.

Jan 1, 1926

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.' Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.' He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.' However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.' In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By H. N. Eavenson

EaRly in 1917, the United States Coal & Coke Co. secured options on several tracts in Harlan County, Ky., aggregating about 19,000 acres in area, and after careful prospecting by outcrop openings and diamond drilling, completed the purchase late in July of that year. This property is situated in the eastern end of Harlan County, south of the Poor Fork of Cumberland River, and extending across Big Black Mountain to the Clover Fork of Cumberland River, a distance of about 7 mi. (11.3 kg.). It extends from the Kentucky-Virginia line westward for about 6 mi. Looney Creek, which empties into Poor Fork, crosses the property for about 4 mi. (6.4 kg.), and as several of the seams within the property outcrop along this stream, it afforded an easy, and the logical, place for development. The property is on the northern side of the geological trough formed by the uplifting of Stone Mountain, on the southern, and Pine Mountain, on the northern side; the northern boundary along Poor Fork is practically at the base of Pine Mountain. This area has been described in various geological reports. The main seam on this property is the one known variously as the "C," Benham, Keokee, Taggart, and Roda; it is also called, by the Kentucky Geological Survey, the Kellioka seam of the western portion of Harlan County. This seam averages, in this property, about 5 ft. (1.5 m.) in thickness, although local rolls reduce this thickness considerably over small areas, and at the extreme western end of the property the seam splits. It is usually clean, although occasionally a small parting occurs within a few inches of the bottom of the seam; it is one of the best coking and gas coals in the United States. The average analysis of this coal is given in Table 1.

Jan 1, 1922

For the benefit of those of our members who are considerable holder; of securities, but owing to their isolated situations are not in close touch with the metropolitan market and current quotations, we are publishing two very interesting graphs, showing the course of the bond and stock markets in New York over a long period. These graphs are-fui?riished through the courtesy of the financial department of the New York Tribune.

Jan 8, 1919

By K. Fallenius

Since 1970 a new series of pneumo-mechanical flotation machines has been developed by Outokumpu Oy. The cells have a completely new type of mechanism based on a recently-developed theory of conditions necessary for dispersion of large amounts of air. The mechanism was developed in 3 cu m cells and scaled to 16 cu m cells. Rotor and stator description, scale-up theory, and practical experience with the 16 cu m cell are presented.

Jan 1, 1976

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 Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of&apos; carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,&apos;-&apos; it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;&apos; the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970

By D. C. Ganow, N. J. Grant, I. R. Silver, A. R. Chaudhuri

The structural changes that result when a metal is "cold worked" lead to higher values of yield and tensile strength on subsequent deformation at room temperature. Further it has been shown that the beneficial effects of cold work are, to some extent, maintained even at elevated temperatures. The strength improvements from prior cold work decrease as the temperature is raised and are a function of grain size, amount of cold work, and strain rate (or time of test). If recrystallization occurs during test, the cold-worked material may even show weaker stress-rupture properties than the annealed material. A question that arises is whether there is a significant effect on the subsequent creep behavior if the prior deformation is performed under creep conditions at high temperatures not too different than the test temperature, but at significantly different strain rates and for various amounts of strain. An answer to this question was sought in the work described in the present paper. PROCEDURE Two materials were used in this work, high-purity aluminum and a solid-solution A1 2 pct Mg alloy. The compositions are shown in Table I. The grain size in the two materials was 0.2 to 0.3 mm. The deformation for both the prestraining and for the creep tests was at constant stress. The procedure adopted was to prestrain a specimen to the desired elongation, remove the load, and cool to room temperature rapidly by spraying. the test bar with cold water. The specimen was then placed in a creep machine, held at the test temperature for less than 5 min, and loaded. Less than 15 min was required to bring the specimen to temperature. The creep stress was based on the diameter resulting from the prior strain, and values of elongation at fracture listed in the tables do not include the respective elongations resulting from the prestrain. The choice of the stresses for the prestrain and for the creep tests was made so that the tests could be completed in relatively short times to maximize any effect of prestrain. The specimens had a gage length of 1 in., the pure aluminum specimens having a diameter of 0.150 in. and the alloy specimens a diameter of 0.125 in. For pure aluminum, prestrain was at 400&apos; and 600°F with testing at 500°F; for the alloy, prestraining was at 700°F and testing at 600°F. RESULTS The prestrain conditions for the aluminum and the alloy specimens are shown in Tables I1 and IV. In addition to showing the time required to achieve the desired prestrain, the expected rupture Lives are given which would have resulted had the creep prestrain been continued to fracture. The prestrained and the annealed specimens were then tested in creep to fracture; the temperature and stress for the pure aliminum specimens being 500o F and 1800 psi and for the alloy, 600&apos; F and 3400 psi. The creep curves for the prestrained and the annealed specimens of pure aluminum showed all three stages of creep; hence in addition to the effect of prestraining on the rupture life, it was also possible to determine the effect of prestraining on the minimum creep rate, and on the time and elongation at the end of each of the three creep stages. The results are shown in Fig. 1 and Table 111.

Jan 1, 1960

By A. Gemperle

Electron diffraction and transmission electron microscopy on foils at room temperature were used to investigate the ordering of Fe-Si alloys containing 10 to 23 at. pct Si. A certain degree of DO3 order was found in all alloys. With the exception of the lowest silicon concentration for which the antiphase domains could not be clearly resolved, the alloys have a domain structure of two-domain type with boundaries having 1/4a01<111> displacement vectors for less than 12.3 at. pct Si and with boundaries having 1/2 a0<100> displacement vectors for more than 12.3 at. pct Si. The alloys with 12.3 at. pct Si have a domain structure consisting of fine domains with 1/2a&apos;o<100> boundaries within much larger domains with 1/4a&apos;o<111> boundaries. The development of these structures can be explained by transition of the alloy from the disordered state into the B2-type order and then into the D03-type order by the mechanism proposed previously for the FeSAl alloys. The existence of the B2 structure in the lower part of the investigated concentration range reported in some articles can be explained by fine domains with 1/2a&apos;o<100> boundaries formed by several disordered planes within large domains with 1/4a&apos;o<111> boundaries. The ordered structure predicted by the theory —with practically no domain boundaries —is found in the alloys having 12.3 at. pct Si where it develops in the B2 structure region. ORDERING in Fe-Si alloys was first studied by phragmenl who found that beginning with 13 at. pct Si the DO3 (Fe3Si) superlattice reflections appear in the diffraction patterns. The equilibrium diagrams constructed later by corson2 and Haughton3 from various measurements proposed the existence of a homogeneous solid solution (a phase) in the range from 0 to 25 at. pct Si. Jette and Greiner4 and Farquhar et al.5 measured the relation between lattice parameter and composition and they considered the break in the curve at 9 to 10 at. pct Si to be caused by the ordered solution a"(Fe3Si). Glaser and Ivanick6 Determined critical ordering temperatures of the alloys containing from 10.9 to 27.9 at. pct Si from the measurement of the electric resistivity of quenched samples. In all cases the critical temperature was lower than the melting point and it was highest for 25 at. pct Si. Lihl and Ebel7 measured the lattice parameter curves at various temperatures up to 1000°C. The region between two breaks on these curves, corresponding to 10 to 12.5 at. pct Si at room temperature, was considered by them to be two-phase (a + a"). They concluded by extrapolation of the measured values that a" in the alloy having 25 at. pct Si is stable up to the melting point. Davies8 studied superlattice reflections in the X-ray diffraction patterns of an alloy containing 8.7 at. pct Si. He found the B2 structure and short-range order in the slowly cooled samples and the DO3 A. GEMPERLE is Research Scientist, Institute of PhysicS, Czechoslovak Academy of Sciences, Prague, Czechoslovakia. __Manuscript submitted January 2, 1968. IMD structure in the quenched and annealed samples. This investigation first reports the presence of the B2 structure, phase a&apos;: in Fe-Si alloys. Meinhardt and krisement9,10 also found its existence in Fe-Si alloys by neutron diffraction. No order was detected by them in the alloy containing 8 at. pct Si. The onset of B2 order was observed at a composition of 9.2 at. pct Si. They found almost perfect B2-type order with partial DO3-type order at room temperature in the 10 to 12.5 at. pct Si range and almost perfect DO3-type order in the 12.5 to 25 at. pct Si range. They established the critical temperatures Tc of both the structures through measurement at higher temperatures. The critical temperature for the B2 structure was found to be always higher than the critical temperature for the DO3 structure of the same alloy. They extrapolated the curves of the critical temperatures and concluded that the alloys with more than 17 at. pct Si have the B2 structure up to the melting point and the alloys with more than 23 at. pct Si have the DO3 structure up to the melting point. The results of Meinhardt and krisement9,10 were confirmed by Dokken&apos;s measurement" of the temperature dependence of the electrical resistivity in the 10.8 to 15 at. pct Si range. On the other hand chessin12 detected by X-ray diffraction a considerably lower degree of order in the 12.7 at. pct Si alloy. ANTIPHASE DOMAIN STRUCTURE IN ALLOYS WITH B2- AND DO$-TYPE ORDER The ordered structures B2 and DO3 can be described in terms of a subdivision of the bcc lattice into four fcc sublattices with a parameter double that of the bcc lattice. Following Marcinkowski13 we will label them I. 11, 111, IV. The B2 structure in the AB alloy is formed by placing A atoms on sublattices I and II and B atoms on sublattices III and IV. In a non-stoichiometric perfectly ordered alloy having concentration (A) > (B), A atoms occupy sublattices I and 11. and A and B atoms distributed at random occupy sublattices III and IV. The DO3 structure in an A3B alloy is formed by placing A atoms on sublattices I, 11, and 111, and B atoms on sublattice IV. In a nonstoichiometric, perfectly ordered alloy having concentration (A)/3 > (B), A atoms occupy sublattices I, 11, and 111, and A and B atoms distributed at random occupy sublattice IV. As further shown in Ref. 13, two types of domains are possible in the B2 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4 a&apos;o<ll1> only. Four types of domains are possible in the DO3 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4a&apos;o<111> and 1/2a&apos;o<l00>. Bethe14 suggested on the basis of theoretical considerations that in a structure with two sublattices at low temperatures only one domain should be present in the whole crystal at equilibrium. Similarly Bragg15 concluded that at low temperatures the domain struc-

Jan 1, 1969

By C. S. Brooks

Several of the commonly used methods for deter-mination of effective grain densities of minerals have been evaluated for accuracy and precision, and their applicability to various types of petroleum reservoir minerals tested. Consideration was given to the effect of consolidation, swelling clay, and wettability on these grain-density determinations. Procedures with helium displacement, a modified low-pressure Boyle&apos;s law porosimeter, and liquid displacement (water, n-decane, and n-octanol) were tested. The helium-displacement procedure was used primarily as an independent reference for which the effects of fluid-solid interaction, e.g., adsorption and wettability, were negligible. The procedures with the Boyle&apos;s law porosimeter and with liquid displacement are the methods in common use. Minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The number of samples tested, while not large, was adequate to permit application of statistical methods. Grain-density measurements on calcite (Iceland spar) provided a basis of comparison for the accuracy and precision of the procedures under investigation for a material with a high degree of chemical and physical homogeneity and for which fluid-solid interactions were at a minimum. Liquid-displacement procedures (water or n-decane) provided the greatest reliability and precision for measurement of the grain densities of the limestone tested. Gas-displacement procedures (helium or Boyle&apos;s law porosimeter) provided the greatest reliability and experimental convenience, if not the greatest precision, for the measurement of the grain densities of the swell- ing clay, Wyoming bentonite, and the shah sandstones which -contained appreciable amounts of swelling, in-terstitial clays. These experiments were designed to evaluate the applicability of the grain-density procedures in common we to some of the less tractable minerals—tight limestones, shaly sandstones, and swelling clays. The results should provide a useful basis for a selection of the method most suitable for application to the various petroleum reservoir minerals encountered and especially for use in the estimation of formation porosity. INTRODUCTION These experiments were undertaken to evaluate the accuracy and precision of several commonly used methods for determination of effective grain densities of minerals, and to test their applicability to various types of petroleum reservoir minerals. Consideration was also given to the effect of consolidation, clay, and wettability on these grain-density determinations. Procedures used included measurements with helium displacement, with a modified low-pressure Boyle&apos;s law porosimeter, and with liquid displacement (water, n-decane, and n-octanol). The minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The accurate determination of the porosity of petroleum reservoir formations, in particular those of low porosity, has received much attention. Both bulk-volume and grain-volume measurements necessary in the evaluation of porosity have been examined by many investigators with the objectives of improving both the accuracy and the precision of these determinations. In this investigation statistical criteria for selection of the most reliable and suitable procedure for use with a given type of mineral are demonstrated. The grain-volume measurement procedures appear to be the most susceptible to improvement.

Jan 1, 1958

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman&apos; reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser&apos; reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,&apos; values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,&apos; on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.&apos; When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,&apos; the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O&apos;Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie&apos; has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970