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By H. R. Babitzke

The purpose of this investigation was to evaluate the potential of columbium-hafnium alloys as structural materials for use at elevated temperatures. The work described in this report was conducted to determine the properties of columbium-hafnium alloys and to select the more promising ones for further improvement. Properties determined in this report were machinability, hardness, workability, tensile strength, and oxidation resistance. Ten ingots, ranging from 100 percent columbium to 70 atomic-percent hafnium, were prepared and subjected to tests. The test results showed that the alloys with 33 and 50 atomic-percent hafnium were superior in workability, strength, and oxidation resistance. For the alloy series tested, the strength and hardness values increased with the increasing hafnium content. Maximum values were reached with 50 atomic-percent hafnium. The oxidation resistance was poorest at the 1 atomic-percent hafnium level but improved with increasing hafnium content through 70 atomic-percent. Eight of the ten ingots were fabricable at room temperature. The two remaining ingots, those with 5 and 10 atomic-percent hafnium, required hot-working.

Jan 1, 1962

By Harold Margalin, Elmars Ence

M. H. Mueller, M. V. Nevitt, and H. W. Knott (Argonne National Laboratory)—We have reported1 the crystal structure of Ti2CU as body centered tetragonal with a. = 2.944A and co = 10.786A, six atoms per unit cell, and space groupl4/mmm(MoSi2 type). This cell is larger but definitely related to the unit cell reported by the authors. It permits definite positions for the titanium and copper atoms in the cell located as follows: 2 Cu (a) 0 0 0; 1/2 1/2 1/2 4 Ti (e) 0 0 z; 1/2 1/2 1/2 + z; 0 0z; 1/2 1/2 1/2- z where z = 0.341 The face centered tetragonal cell reported by the authors can be transformed to a small body centered tetragonal cell with flo (small bet) = ao(fct)v2 Both unit cells have the same CO. Neither the face centered tetragonal cell with four atoms per unit cell nor the small body centered tetragonal cell with its two atoms per unit cell lend themselves conveniently to an orderly arrangment of the 2 to 1 ratio of titanium to copper atoms. When the co of this small body centered cell is tripled, however, a large body centered tetragonal cell results with six atoms per unit cell as described above. We had also noted that the X-ray patterns of Ti2Cu indicated that the structure could be approximately described by the face centered tetragonal cell as reported by the authors; how- ever, there was evidence for a few additional very weak lines whose positions indicated a larger unit cell. Since the X-ray scattering amplitudes of titanium and copper are nearly equal, it is evident that it is difficult to distinguish their positions especially from X-ray powder patterns. It was therefore decided to look at a powder pattern obtained by neutron diffraction since the scattering amplitudes of the two elements are considerably different in magnitude and opposite in sign. The sample used for neutron diffraction was selected from a group of three alloys prepared by arc melting using crystal bar titanium of 99.92 pet nominal purity and 99.999 pet pure Cu. The alloys designated as A, B, and C had the following respective compositions: Ti-32.8 at. pet Cu, Ti-33.3 at. pet Cu, and Ti-33.8 at. pet Cu. On the basis of the melting losses incurred, it was established that the actual concentration of either component in any of the alloys probably did not deviate from the intended value by as much as 0.1 at. pet. The alloys were annealed for 5 days at 700°C in evacuated Vycor capsules and quenched in tap water. The metallographic structures of these alloys are shown in Fig. 1. None of the alloys contained sufficient second phase to permit its positive identification. Since alloy B contained the least amount of second phase and since its composition placed it closest to the ideal stoichiometry, it was chosen for the neutron diffraction study. The oxygen content of alloy B was found by chemical analysis to be 0.06 at. pet. This particular intermetallic compound is especially suitable for investigation with neutron diffraction since if the titanium and copper atoms have a random statistical distribution, a near null-matrix would result in which there would be practically no coherent scattering of neutrons, and hence no Bragg diffraction peaks. Such a condition could come

Jan 1, 1962

By H. O. Seigel

Induced Polarization includes many types of dipolar charge distributions set up by the passage of current through consolidated or unconsolidated rocks. Among its causes are concentration polarization and electrokinetic effects in all rocks and the phenomenon of Overvoltage in rocks containing electronic conductors such as metallic sulphides and graphite. In normal rocks the polarization effects may be usually con-fined within relatively narrow limits and any large departures may be at-tributable to the presence of electronic conductors. In practice, Induced Polarization is measured in one of two ways. In the first a steady current of some seconds duration is passed and abruptly interrupted and the slowly decaying transient voltages existing in the ~round are measured after interruption. This is known as the "pulse", "transient", or Direct Cur-rent Induced Polarization (D.C.I.P.).The second method entails a comparison of apparent resistivities using sinusoidal alternating current of two or more frequencies, generally within the range of 1/10 to 10 c.p.s. Induced Polarization extends the

Jan 1, 1962

By E. W. Lucht

THE term "high pressure", as used in industry today, is applied rather loosely. Generally, it refers to pressures that are higher than those encountered in most industrial processes although no definite limits are normally stated. For the purpose of this talk I should like to set rather arbitrary limits to the term "high pressure", and in ab-solute figures this would be the range from 1000 psi to perhaps 40,000 or 50,000 p.s.i. The scope of high pressure technology is very broad, and it would take more time than we have avail-able here today to cover fully even one aspect of the field. Therefore, I should like to discuss just some of the techniques used and problems en-countered in high pressure operations. Research work into the high pressure region dates back about 150 years, but it was not until 1910 that the first commercial application of high pressure technology was made in the production of ammonia.

Jan 1, 1962

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By P. Chollet, A Constant

THE RESULTS of a previous investigation ( 1) on the work-softening of some heat-treated steels have led to the conclusion that the occurrence and intensity of the phenomenon is possibly governed by the work-hardening capacity of the material, and the relative amount of retained austenite. The first assumption is compatible with Polakowski's theory (2) that the absence of work-softening, in steels quenched and tempered at relatively low temperatures, may be attributed to the high rate of work-hardening which compensates for, and even out-weighs, the loss of internal energy associated with the simultaneous rearrangement of the original system of internal stresses. Indeed, Polakowski first considered the work-softening as a manifestation of a partial release (by cold-working) of the latent strain energy stored in

Jan 1, 1962

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By A. G. Loomis

METHODS for measuring relative permeability as a valid function of saturation were compared by the. Bureau of Mines, using core samples from representative oil-productive California formations, from the Bartlesville sand in Oklahoma, and from synthetic samples. Measurements for gas-oil systems were made by steady-state dynamic, unsteady-state displacement and two stationary-phase methods. Measurements for water-oil systems were made by the unsteady-state displacement method. As the ratio rather than individual relative permeabilities is measured by the last method, three methods for calculating individual relative permeabilites from their measured ratio were compared for gas-oil systems and two methods for water-oil systems. Errors arising from capillary discontinuities, such as the end effect and stabilized-zone flow, are discussed and evaluated; possible errors rocs arising from turbulant flow are also examined. The inapplicability of non-steady-state methods for water-oil systems that are not definitely oil-wet is discussed in detail. Measurements of relative permeability to both gas and oil can be made quickly and accurately by the steady-state dynamic method when rates of flow of the two phases are sufficient to minimize the capillary discontinuity at the outflow end of the sample. At such rates relative permeability-saturation measurements are essentially independent of the rate of flow. The steady-state method wits modified by a dispersion section at the inflow end of the sample acid designated tie dispersed-feed method.

Jan 1, 1962

By Heinz W. Sternberg

The literature on electrochemical treatment of coal is reviewed, and possible avenues of further research in this field are discussed in this report. Electrolytic reduction of finely distributed coal resulted in the addition of as many as 9 atoms of hydrogen to 100 atoms of carbon. Reduction of coal extracts at controlled potentials indicated the presence of condensed aromatic hydrocarbons and reducible quinones in coal. As much as 65 percent of low-rank coal can be made alkali soluble by electrochemical treatment. Higher rank coals gave smaller yields of alkali-soluble products. However, the nature of this reaction is not clear. The difficulty of reducing coal electrolytically is probably due to the insolubility of coal and not to any structural peculiarity. Reduction of coal by electrolytically generated radical anions appears to be a promising approach for further research.

Jan 1, 1962

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.' In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.' Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By M. J. Langley

Zinc ores were first discovered in Tennessee in 1856 at Jefferson City where a deposit of oxidized ore became known as the Mossy Creek Mine. From that time until 1913 small scale attempts at prospecting and mining were made in various parts of the district. The actual systematic development of the zinc deposits dates from 1913 when the American Zinc Company started operations at Mascot. Six mines are in operation by three companies and a seventh mine is being developed by a fourth company. The total daily production from the field is 11,000 tons of crude ore, which grades from 3 to 6 per cent zinc. Most of the ore bodies are large and ramiform, resembling asyrmetrical networks in which the ore shoots form channel like branches with areas of non-comercia1 rock, called blank islands. Most of the orebodies are adapted to large scale mechanization.

Jan 1, 1962

By W. Kunda, J P. Warner

SHERRITT GORDON Mines Limited annually produce 300,-000 pounds of pure cobalt by processing a nickel-cobalt-copper-iron sulphide ore which is mined at Lynn Lake, Manitoba. The ore (containing 0.04 per cent Co) is •concentrated to give a concentrate containing l 1-12 per cent nickel, about 2.0 per cent .copper, and 0.25-0.35 per cent cobalt, which is treated at the Refinery in Fort Saskatchewan, Alberta. The concentrate is leached in an ammoniacal solution of ammonium sulphate using compressed air as the oxidant. After filtration the leach solution contains, besides nickel and cobalt, copper ammines, sulpharnates and salts of various thionic acids. The copper is removed by precipitation as sulphide and the sulphur compounds converted to ammonium sulphate by a combined oxidation and hydrolysis treatment. The purified solution •Containing about 45 gpl of nickel and 1 gpl of cobalt is treated with gaseous hydrogen under pressure at 350°F to precipitate metallic nickel powder, the precipitation 'being terminated when the nickel content of the solution is about 0.8-1 gpl. Only about

Jan 1, 1962

By J. R. Nettle

The development of a process for upgrading offgrade titanium metal by electrorefining in molten salt led to an investigation of the electrotransfer characteristics of selected metals when alloyed with the titanium to be refined. Previous tests on seven binary titanium alloys showed that the degree of transfer of the alloying constituent depends on the constituent and on the operating procedurese.5 This report describes tests on electrorefining ternary mixtures of titanium with selected metallic elements. Ten alloys were prepared from high purity titanium and 2-1/2 percent of each of the metal pairs selected from the same elements used in the binary study; manganese, vanadium, chromium, zirconium, tin, molybdenum, aluminum. Operating variables were similar to those investigated in the binary alloy study that gave minimum alloy metal transfer. The data presented indicate the transfer characteristics of the various metals and combinations tested relative to each other.

Jan 1, 1962

By A. M. Gaudin, T. P. Meloy

This paper presents the theoretical derivation of the distribution equation for single fracture. The equation is shown to accord with experiment. Several empirical size-distribution equations have been proposed to describe the size of broken materials. Among them are the Gaudin-Schuhmann equation and the Rosin-Rammler equation.3*4 The Gaudin-Schuhmann equation relates the relative fraction of undersize to relative size —. In this relationship Mo is the total weight of crushed sample, M(x) the weight of undersize contained, x the size considered, K a quantity called the size modulus, which together with the slope parameter, m, characterizes the product. The slope parameter is usually close to unity. The Rosin-Rammler equation relates the same relative fraction of undersize to the relative size modulus by an equation of different form In this relationship, e is the base of natural logarithms. In the fine size-range when m is unity both equations give Gilvarry and Berstrom have sought a size distribution equation having a sound theoretical basis. They have come to an equation taking into account the effect of volume, surface and edge flaws in fragmentation. If the effect of the volume and surface flaws is neglected, the equation taking only edge flaws into account has the form of the Rosin-Rammler equation. In the present paper, a theoretical size-distribution

Jan 1, 1962

By G. L. Hopps

Various chemicals, including compounds of copper and lead, were added to a mixture of No. 2 and No. 6 fuel oils that was fired in an experimental furnace. Tests were made to determine (1) the effectiveness of these chemicals in removing soot deposits on probes devised to simulate heat-transfer surfaces in boilers and (2) the effectiveness of the chemicals in preventing the deposition of soot on the probe surface. Test conditions were regulated so that the temperature of the products of combustion adjacent to the probes was in the range of 625° to 700° F. The clean-metal temperatures of the air-cooled probes were comparable with the water-tube temperatures in boilers operated at 40 to 100 p.s,i.g. The dosages of the fuel oil additives used in these tests were generally larger than those usually recommended for most proprietary compounds.

Jan 1, 1962

By R. W. Kraft

A comprehensive analysis of the crystallographic and metallographic structure of several Al-CuAl, lamellar eutectic grains solidified under equilibrium conditions has been performed. A consistent pattern was discovered which was interpreted in terms of a detailed atomistic model of an interface describable as: Interface II {111} AL 11 {211} <101>Al <120> ? Several arguments are presented to substantiate the theory. It is compared in detail with another interface model characteristic of the Wid-manstatten precipitate of CuAl2 in A1 at low Cu levels. In addition, a concept is proposed to help explain the structure of the compound CuAl2. It has been shown that the eutectic alloy between A1 and CuA1, can be forced to solidify as substantially parallel lamellae throughout a relatively large volume&apos; by appropriately controlling the solidification parameters of growth rate, thermal gradients, and impurity level and by causing solidification to proceed in a unidirectional fashion from one end of an ingot to the other. A typical ingot solidified in this manner shows three distinct zones along the length of the ingot, Fig. 1. At the head end is a region consisting of many different grains, some of which are elongated slightly in the direction of solidification. After a few centimeters of growth, this polygrained region gradually merges into the second zone which consists of a very few elongated coarse grains. The third zone at the tail end is a region of eutectic colonies caused by segregation of impurities. Microscopic examination of transverse and longitudinal sections of the ingots reveals that during the initial stages of growth (zone I) the lamellar structure is frequently highly distorted and twisted but that it straightens out in zone 11. This characteristic pattern suggests that nucleation of a eutectic grain begins randomly at the head end of the ingot, and that some particular orientation relationship between the phases is more favorable from an energy consideration than others for one reason or another, so that some grains grow and others which are less favorably oriented do not. The favorably oriented or "low energy" grains continue to grow until excess solute rejected at the advancing liquid-solid interface destroys the parallel lamellar structure by forming a cellular rather than a substantially planar interface. When this occurs, the parallel lamellae fan out and eutectic colonies are formed because the lamellae grow perpendicular to the local interface. Questions naturally arise as to the crystallographic nature of the "low energy" grains. What do the grains which persist into zone II have in common? Can this explain the stability of such grains during growth? To answer the first question it is necessary to determine the crystallographic orientation of the lamellae of each phase relative to one another. This has been done for Al-CuAl2 eutectic alloys by two different techniques on specimens prepared in different ways.2&apos;3 The results were different from each other and from a third orientation relationship between A1 and CuA1, reported for overaged A1-Cu alloys.4 The three orientation relationships are summarized below to illustrate their similarities and their differences. (001) ? 11 (001) A1; [l00] ? 11 [l00] Al Eutectic, Ref. 2 (001) 8 1) (001) A1; [1001 ?11 [1101 A1 Eutectic, Ref. 3 (001) ? 11 (001) A1; [l00] ? 11 [310] Al; Widmanstfitten, Ref. 4 It is not surprising that different orientation relationships were found by Ellwood and Bagley,&apos; and Takahashi3 since the solidification conditions were quite different. Nor is it surprising that Mehl, Barrett, and Rhines 4 found still another value since they were studying another type of alloy. Nevertheless, it would be expected that some logical and systematic pattern could be found if all the alloys were at equilibrium since the same two phases are

Jan 1, 1962

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.&apos; Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By D. Kuhlmann-Wilsdorf

A new theory of work hardening is developed which rests on only a few simple principles and is applicable to a wide variety of materials and dislocation structures. It explains, qualitatively, the general characteristics of the three-stage shear stress-shear strain curve of fcc metals, as well as the most important features connected with easy glide. The value of, the work-hardening coefficient in stage 11, is derived quantitatively, from first principles, and is shown to be insensitive to many changes in detailed dislocation behavior. The low rate at which energy is stored during mechanical working in stage 11, the dependence of slip line length on stress, and the so-called Cottrell-Stokes law are explained. Although the theory is primarily developed for fcc metals and alloys, it is largely applicable also to some other materiuls, and in particular apparently to poly crystalline simple steels in theh linear range of hardening. FOR pure fcc metals and alloys, after many different pretreatments and under a great variety of testing conditions, the well-known three-stage work-hardening curve is commonly observed. Moreover, the work-hardening coefficient in stage 11, 011, bears an almost constant relationship to G, the modulus of rigidity, such that K = G/Brr" = 300, within a factor of about 2 either way. The very fact that the three-stage curve and the value of K are so very persistent, can hardly be understood except on the assumption that some quite simple phenomena are responsible. In this light all available theories of work hardening must be judged unsatisfactory: Each of them is based on some quite specific dislocation model, while it is known that metals with similar values of K may have widely different dislocation structures, for example, dislocation tangles in the case of pure fcc metals, and piled-up groups of dislocations in a-brasstype alloys. Thus, while a particular theory might conceivably represent a special case with a reasonable degree of accuracy, it cannot possibly have illuminated the underlying principle. Another severe criticism applying to the presently most widely discussed theories is that they employ empirical or even quite unexplained parameters in order to arrive at a numerical value of K. This indicates that some vital aspect of the work-hardening process has remained unexplained. In the present paper, a new theory of work-hardening is developed which does not suffer from the above shortcomings. It is derived from first principles, and is founded on the realization that the underlying causes for the three-stage work-harden- ing curve and for the persistence of the numerical value of O,, must be few and simple. As a first step it is shown herein that the experimental oklservations on "easy glide" can be explained on the assumption that in this stage dislocations multiply, beginning in a number of restricted area:;, and from there penetrate into crystal regions still substantially free of glide dislocations until a quasi-uniform dislocation distribution has been established. During "easy glide", the resistance to the movement of the foremost dislocations, advancing into still largely a dislocation-free regions, is believed to control the flow stress. This resistance is determined by various factors, among them the reaction of the dislocations against bowing-out into loops, which is due to their line tension. Without such bowing-out no dislocation multiplication would occur, but the corresponding contribution to the flow stress stays practically constant all through stage I. According to the present theory, stage TI begins as soon as there are no more areas left into which newly formed dislocations have not yet penetrated, i.e., as soon :is a quasi-uniform dislocation density has been attaned. Regardless of how, in detail, the dislocations should happen to be arranged at the end of "easy glide", whether in pileups or tangles, on one glide system or on several, the stress necessary to overcome the line tension of the segments must now increase, because the dislocation density increiises while the average free dislocation length decreases. It is argued that all other contributions to the flow stress stay at about the same level as in stage I, and that the said increase in the stress necessary to bow out dislocation segments into loops is responsible for the major part of work hardening in stage 11. Stage TII of the stress-strain curve is explained by largely follouing the ideas of Seeger and his co-workers; however, it is pointed out that the start of stage m may on occasion indicate the onset of "conservative climb" instead of cross slip. Indirect evidence indicates that linear work hardening persists even under the profuse action of cross slip, but at a lower rate. Only when, in addition to cross slip, climb operates extensively, does the work-hardening rat,. drop sharply, ultimately down to zero. BRIEF SURVEY OF EXPERIMENTAL EVIDENCE The stress-strain curve of crystals of many different substances are qualitatively similar. No significant permanent plastic deformation takes place below the so-called "critical resolved shear stress". As the applied stress is raised beyond this level. yielding occurs with little or no work hardening and

Jan 1, 1962

By D. J. Brown

Froth flotation is now used to recover millions of tons of fine coal,(-1/2 mm), every year. For example, in Great Britain, 4-million tons of flotation concentrate was produced in 1960, about 3% of the mechanically cleaned out- put and 2% of the total salable output. Coal flotation is not so widely practiced in the U. S. as it is in Europe since much American coal occurs in thick seams of high grade and does not require cleaning. However, in the U. S., as elsewhere, the increasing mechanization of coal mining machinery has lead to a lowering in size and grade of product from the mine and to an increasing need for cleaning of coal to improve the grade before sale. With an increasing proportion of fines in the product, froth flotation has assumed a greater importance as a cleaning process for coal. In the last three years, over 40 flotation plants have been put into operation in the Appalachian area of the U. S.80 Fine coal recovered by means of froth flotation may be used as a powdered fuel alone or mixed with coarser grades. The removal of this fine coal from washery water makes possible the recirculation and re-use of the water and also leads to improved and more consistent operation of jigs and other separating machines which function less effectively when there is a build-up of fine solids in the washery water. Finally, froth flotation is of assistance in the production of a clarified effluent which may be discharged from the washery without polluting local rivers, streams, or wells. The 1961 cost of installing a new coal flotation plant in Great Britain would be about $19,000 per ton of dry solids input per hour, including the cost of new buildings and coal and shale filtration and water clarification equipment. The figure for the gravity concentration of the large coal, the main plant, would be about $4,800 per tph. The operating cost for the new coal flotation plant would be about $1.10 per ton. Even at this level of cost the cleaning operation is economic in Great Britain for coking coals. In the U. S., a froth flotation cost of 14$per ton of cleanfilter cake was quoted early in 1958 for one operation,l though admittedly this was a special case. Assuming a cake moisture con- tent of 30%, it is estimated that this cost is equivalent to a figure of 256 per ton of dry solids input, for the incorporation of coal flotation in an existing washery. A cost oh 416 per ton of concentrate was quoted76 in a recent analysis of flotation economics, this cost being brought up to $1.11 per ton after payment of royalty, welfare and association dues and taxes. Capital cost was $120,000 for a plant producing 133 tpd of concentrate. Before considering the treatment of coal by flotation it is appropriate to survey some of the properties of coal which are of importance in the process.

Jan 1, 1962

By Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.&apos; This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2&apos;6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7&apos;9 These effects were observed at testing temperatures in the range 100 to 300&apos;. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.&apos; These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180&apos; was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio &apos;c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962