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By Renato G. Bautista, Robert A. Hard

A comparative study has been made of the ex-tractability of several of the transitim metals from thiocyanate sohtions using methyl isobutyl ketone as the organic solvent. Extractions were made of scandium (III), chromium (III), manganese (II), iron (III), and cobalt (II), of which only the scandium , iron, and cobalt were readily extracted. All extractions were made at pH 2 and at 25.5 °C. A series of extraction experiments was made on scandium, iron, and cobalt to determine the effect of thiocyanate cmcentration added as the ammonium and also as the calcium salt. Also determined was the effect of metal ion concentratim and ionic strength on the distribution ratio. Analyses of the organic extracts indicated the scandium and iron were extracted principally in the uncharged trithiocyanate form, while the extractable form of the cobalt contained the cobaltotetrathiocyanate anion. THE chemical separation of metal complexes in solution by solvent extraction has in recent years been developed for large scale separation as well as bench scale work in the laboratory. It has also found increased application in analytical chemistry. Its extension to extractive metallurgy as a unit operation is best illustrated in the recovery of uranium and vanadium from their leached liquor.5-8 The extractability of some thiocyanate systems have been extensively investigated. The rate earths have been separated from one another using butanol as a olvent. Scandium was effectively extracted in ethyl ether using ammonium thiocyanate as the com-plexing agent.'' Similarly, the separation of hafnium from zirconium has been reported using ether""' or hexone13 as the organic solvent. The extractability of various metal thiocyanates in ethyl ether is given by 0ck.l Sharp and Wilkinson15 prepared nickel-free cobalt slats by thiocyanate extraction. The mechanism of extraction of titanium (IV) thiocyanate with methyl isobutyl ketone was determined by elafosse.''" The characterization of cobalt (TI) thiocyanate complex using methyl isobutyl ketone as the solvent at near neutral aqueous solution and the spectrometric studies of the ex-tractable cobalt complex has been made by Hard." It is noteworthy to mention at this point that the fundamental characteristic of ketone (oxonium) solvent extraction is that the extractable species are uncharged ion pairs solvated by the ketone molecules, but probably still partially hydrated.

Jan 1, 1963

By T. J. Koppenaal

The surface slip line structure has been investigated by optical microscopy during the easy glide deformation of Cu-A1 single crystals as a function of composition, testing temperature and prior thermal treatment. The slip line structure in alloys of 2.5 or less at. pct Al is similar to pure copper, while alloys of 5 or more at. pct Al show slip tracings typical of a brass. Cross slip is observed in the "a-brass type" crystals and the amount of this type of slip increases rapidly with aluminum content. The cross slip tendency in 14 at. pct Al crystals is signicantly higher when tested at 150°C as compared to 4.2" and 77°K. In addition, cross slip is more pronounced in this alloy in the furnace cooled condition than when quenched from 450°C. The cross slip behavior is analyzed in terms of existing models for this type of deformation. In two previous investigations, reports of yield points1 and solid solution strengthening2 in Cu-A1 single crystals have been given. This paper enlarges upon the brief description of the slip line structure discussed in these reports. Since the easy glide slip line pattern of copper changes markedly with the addition of -30 pct Zn (-brass),3 a study of slip lines as a function of solute additions in Cu solid solutions should help to explain some of these differences. In addition to composition variables, slip lines have also been studied as a function of testing temperature and prior thermal treatment. PROCEDURE The slip line observations were made on single crystals of 0.5 to 14 at. pct Al using a light microscope. Details concerning the preparation and basic testing procedure are given elsewhere.' Prior to testing, each crystal was homogenized at 900°C for 24 hrs, furnace cooled, and electrolytically polished in a 60 pct phosphoric acid solution. The strain rate was-5 X 10 sec-I in each case. Unless otherwise stated, all observations reported upon here were made during the early stages of easy glide. RESULTS AND DISCUSSION The maximum magnification generally used was 1000X, and slip lines could be resolved down to about 105 cm (1000A). This resolution is appreciably less than obtainable with electron microscopy replica techniques where the replication can resolve slip lines down to about 40 A. Thus, while many qualitative features could be studied, the type of quantitative data obtainable with an electron microscopy replica study could not be made. Crystals containing 0.5 and 2.5 at. pct Al deform much like pure copper exhibiting a high density of fine slip lines that cover the entire gage length of the specimens. Fig. 1 shows the surface slip line pattern in a 2.5 at. pct A1 extended 0.01 shear strain at room temperature. Crystals having 5 to 14 at. pct A1 showed appreciably coarser slip lines that were generally concentrated at one end of the gage length. During easy glide these coarse slip lines propagate along the gage length in a manner similar to that observed in a-brass single crystals by Piercy, Cahn, and cottrel14 and refered to by them as a Lüders band propagation. Fig. 2 shows a typical area of these coarse slips in a 14 at. pct A1 crystal after a room temperature shear strain of 0.01. Two slip systems were apparently active. Using a method described by Cullity, the angles, between the specimen axis and the normals of the primary and secondary slip planes were determined to be 50 and 84 deg, respectively. 'From the Laue photograph, was 52, 81, 66, and 30 deg for the primary, cross, conjugate, and fourth slip planes, respectively. The secondary active plane in Fig. 2 is thus established as the cross slip plane, and the operative slip system is evidently the cross slip system, e.g., slip

Jan 1, 1963

Jan 1, 1963

By W J. Dyck

Past attempts to establish an integrated steel industry on the West Coast of Canada have been unsuccessful for at least three reasons: (a) insufficient reserves of a suit-able iron ore supply; (b) a relatively small local market for iron and steel; and (c) the non-availability of an economical process to produce primary iron on a small scale. Today, the reserves of economically mineable ore deposits are ample to support a steel production of 100,000 to 200,-000 tons per annum. The local market has increased so as to be able to absorb most of this capacity. With-in the next few years, a small integrated steel plant, including the "H-Iron" direct iron ore reduction process for electric furnace charge stock production, will be able to show a profitable operation. Introduction

Jan 1, 1963

By W M. Cameron

Geophysical studies have extended seaward in recent years, and the important discoveries which have been made have led to a better understanding of geological processes. A present source of certain minerals, the sea will eventually serve as an important source of desalinated water. The continental helves, in particular, represent a potential mineral resource. The expansion of Canadian oceanographic effort that is now underway will eventually lead to the exploitation of the wealth beneath the sea. THE subject of this symposium, which emphasizes the word "geophysics," the specialties of the speakers who are contributing and the nature of the audience at first made me believe that I, a a physical oceanographer, would be out of place. However, I shall undertake to classify myself as a geophysicist, and shall arrange my remarks on my specialty o that they might be of interest to those of you who are predominantly geologists, metallurgists or mining engineers.

Jan 1, 1963

By Thomas M. Nasiatka

Tests with a high-pressure water jet were conducted in the steeply pitching Roslyn No. 5 bituminous coalbed in the Roslyn No. 9 mine, Roslyn, Wash., to determine the feasibility of extracting coal from pillars and from a solid coal face in development without drilling and blasting. During pillar mining, using a hand-held monitor, the best results were obtained with a 0.150-inch- diameter nozzle, a water pressure of 3,500 psi, and a flow rate of 38.5 gpm.3 The rate of mining and productivity were 0.74 ton per minute and 16.6 tons per man-shift, respectively. During development mining, using a monitor mounted on a roof jack, the best results were obtained with a 0.148-inch-diameter nozzle, a water pressure of 4,500 psi, and a flow rate of 40.0 gpm. In one section of the mine where the coal was relatively hard, the rate .of mining and productivity were 0.10 ton per minute and 5.7 tons per man-shift, respectively in another section of the mine where the coal was relatively soft, the rate of mining and productivity were 0.51 ton per minute and 8.3 tons per man-shift, respectively. The tests showed that hydraulic mining methods were more productive than conventional mining methods in pillar mining. In development the productivity of hydraulic mining depended primarily upon the coal hardness. Compared with conventional methods, hydraulic mining methods were less productive where the coal was relatively hard and equally as productive where the coal was relatively soft.

Jan 1, 1963

By J. B. Darby

In an investigation of various equiatomic alloys of transition elements, Dwightl did not find evidence for the CsC1-type ordered structure in VMn. More recently waterstrat2 has reported the occurrence of this structure in the alloy his sample had been homogenized at 1150°C and subsequently reannealed at 725°C after crushing to powder. The purpose of this note is to confirm the existence of the CsC1-type ordered structure in VMn and to report a lattice parameter. An equiatomic alloy was prepared by arc-melting under an argon atmosphere vanadium and electrolytic manganese having a purity of at least 99.9 pet. The composition was obtained by charging an excess of manganese and monitoring the weight loss until the stoichiometric composition was achieved; the assumption that the loss during melting was due to the vaporization of manganese appears to be a valid one.' The calculated composition of the sample prepared was 49.85 at. pct V and 50.15 at. pct Mn. Specimens taken from the fractured as-cast buttons were wrapped in molybdenum foil and encapsulated in quartz capsules under vacuum; there was no evidence of a reaction between the alloy and foil. The X-ray patterns were obtained using filtered copper or chromium radiation with a Straumanis-type Debye-Scherrer camera having a diameter of 114.6 mm. The CrKa radiation is best suited for detecting the superlattice lines since it overcomes the slight difference in scattering powers of the components by making use of the anomalies in atomic scattering factor which occur when the frequency of the radiation is close to the characteristic absorption frequency of one of the elements.394 A specimen in the as-cast condition, as well as one which had been annealed for 1 week at 900°C and water-quenched, gave a diffraction pattern for the disordered bcc solid solution. However, when samples were homogenized at 900°C for 3 weeks followed by a subsequent anneal at 700°C for 6 to 7 weeks and then water-quenched or furnace-cooled, the (loo), (1111, and (210) Ka superlattice lines were observed in films taken with chromium radiation. An ao = 2.904 * 0.001 was determined by a Nelson-Riley extrapolation from a film taken with CuKa radiation. The author wishes to thank Mr. J. W. Downey and Mr. L. J. Norton for carrying out the experimental portion of this investigation. This work was performed at the Argonne National Laboratory under the auspices of the U.S. Atomic Energy Commission.

Jan 1, 1963

By Jei Y. Choi, P. G. Shewmon

Using a scratch smoothing technique, the magnitude and the ratio of the surface diffusion coefficients (D,) in two orthogonal directions have been measured on copper for over 100 different surface orientations. Anisotropy was found for all surface orientations except those lying near the (100) and (111); however, these anisotropies were rarely greater than 2.0. The direction of maximum D, appears to coincide with the direction of step edges on any given surface, and if no such steps exist, no anisotropy is found. Thus the jump frequency along a step edge is shown to be faster than the frequency of a jump over the step. The values of Ds and AH for the (100) and the (111) orientations agree quite well with those obtained earlier by the grain boundary grooving technique. It is proven that the directions of maximum and minimum D, (the principal axes) for any surface orientation are known if the perfectly ordered plane corresponding to the given surface orientation possesses a plane of mirror symmetry. Thus the principal axes of D, for orientations lying along the sides of the unit stereo-graphic triangle are always known independent of the extent of thermal disorder or impurity adsorption. The merits and shortcomings of King and Mullins' recently published equations relating Ds to the rate of scratch smoothing are discussed. 1N an earlier paper the authors have reported the variation of the surface diffusion coefficient (Ds) with surface orientation on copper.' In that study Ds was determined from the rate of growth of grain boundary grooves on symmetric bicrystals. This gave values of Ds from 850° to 1070°C in a given direction on each of the six surfaces. It was found that the activation energy for surface diffusion was essentially the same for all six surfaces. The theory developed to explain these data assumed that the free energy of any given type of surface site depends only on the number of nearest neighbors the atom has. This same theory predicted that on any given surface Ds should be independent of direction. The primary aim of this study was to check the validity of this prediction for a wide range of surface orientations on copper. The growth of grain boundary grooves is ideal for studying Ds in a given direction on a given surface over a range of temperatures, because the same specimen can be repolished and used again. However, there is considerable work involved in growing a symmetric bicrystal, and for a survey of Ds in two or more directions on many surface orientations, the technique would be arduous. A better technique appeared to be the scratch method used primarily by Mykura. 2 If a scratch is placed in a surface whose surface tension is independent of orientation, the surface will smooth out in time under the influence of surface tension. To determine D, from this flattening, Blakely and Mykura2 used an approximate solution which was assumed to describe the rate of flattening. Recently King and Mullins3 (hereinafter K and M) have given a more exact analysis of the flattening of an isolated scratch. A second aim of this paper was to check the validity of this newer analysis and compare the values of Ds determined thereby with the values obtained from grain boundary grooving techniques. EXPERIMENTAL PROCEDURE In an effort to work with a particular predetermined surface orientation, light orthogonal scratches

Jan 1, 1963

By Edward W. Parsons

Conventional rock-bolt anchors often fail when installed in weak formations. The purpose of this work was to develop an anchor that would utilize an explosive charge to secure anchorage in any type of rock. Laboratory work to develop a rock-bolt anchored by explosive forming was initiated using rock-bolt models which had a drilled explosive chamber and were composed of various metals. This was followed by the use of several types of seamless tubing which were expanded with a water-coupled explosive capsule. By attaching a length of solid bolt to the anchor tube, a prototype explosive-anchored rock bolt was made. More than 150 laboratory models were expanded during this phase of development, During two field tests in underground mines (A and B) and one in an open- cut mine (C), 87 explosive-anchored bolts, 9 slot-and-wedge bolts, 2 bolts anchored with expanding grout, and 28 expansion-shell bolts consisting of three types of shells were installed and subjected to pull tests. The field tests were run to determine the effects of variables such as the amount and placement of the explosive charge, design changes in the bolt, and the effect on anchorage of different pull-test techniques. The field tests revealed the following: Mine A. The explosive-anchored rock bolt was feasible, but changes were necessary in bolt materials and in some details of bolt design. Mine B. The design and materials of the bolt gave excellent results in hard fractured rock, but no information was obtained concerning variations in the dimensions of the anchor unit or in the explosive charge. Nine C. Varying the explosive charge to produce a beaded surface on the bolt tube and tightening of the anchored bolt before pull-testing were found to increase significantly the anchorage obtained in soft ground.

Jan 1, 1963

By F. L. Kadey

The petrographic microscope is a well known tool in nonmetallic materials research. Its utility in the study of perlite is, therefore, not surprising. Valuable information has been derived on samples smaller than those needed by most other methods of analysis. Relatively little has been written about the petrographic analysis of perlite for two chief reasons: perlite is a material of relatively new commercial interest; and the independent prospector or expander, responsible for most studies, attacks the problem from an immediately practical viewpoint. Hence, petrographic studies of perlite have been limited to academic aspects. Rapid development of commercial interest in perlite has changed the situation. Mining and expanding companies now have effective research tools; and such instruments as the petrographic microscope have added materially to practical knowledge about this mineral. Petrographic techniques employed in the search for suitable deposits screen worthless samples rapidly and inexpensively compared with large-scale expanding tests. Hence, only samples of potential quality are selected for further testing. Field appearance of perlite reveals little about its true identity and practically nothing about its commercial significance. Consequently, any method that can be used to separate the "wheat from the chaff" is valuable. In addition to the conventional thin-section and immersion methods used in evaluation of crude perlite, petrographic microscope techniques have contributed to the study of expanded perlite. When apparently similar materials behave as differently in use as perlites, the internal structure of the individual particles becomes a subject of great interest. The purpose of this paper is to discuss some of the petrographic techniques used to characterize this material. WHAT IS PERLITE AND WHERE IS IT FOUND? Perlite was at first described as a glassy rhyolite possessing a pearl-like luster and exhibiting numerous concentric cracks resembling an onion skin appearance.' Fig. 1 is an illustration of perlite in this classical sense. Recently, its definition has taken on a commercial connotation: an acid volcanic containing 2 to 5% of combined water that, when heated rapidly to the softening point of the glass, coincident with the volatilization of the combined water, expands or "pops". Fig. 2, although hardly fitting the classical description given by Johannsen, is an excellent perlite in the commercial sense. It may occur as a breccia in rhyolite, (Fig. 3) and sometimes it is associated with obsidian nodules, as illustrated in Fig. 4. The term perlite includes the expanded product also. In the United States, perlitic rocks are restricted to the western part of the country. 2 Elsewhere in the northern hemisphere, European occurrences follow a belt beginning in Iceland and extending in a southeasterly direction through Scotland, County Antrim in Northern Ireland, and through the Massif Central of France, Germany, and Hungary; thence, into Italy and Sardinia, and through some of the Aegean Islands. A general oriental belt extends from Japan through Australia and New Zealand. Rhyolitic areas elsewhere in the world undoubtedly contain perlite.

Jan 1, 1963

By L. B. Pankratz

The heat contents of the sesquioxides of erbium, holmium, thulium, and ytterbium (Er203, Ho203, Tm203, and Yb203) in the cubic crystalline form were measured over the temperature range from 298° to 1,800° K. The erbium and holmium sesquioxides gave regular heat content-temperature curves. Thulium sesquioxide had a minor thermal anomaly near 1,680° K, with a heat absorption of 310 cal/mole; similarly, ytterbium sesquioxide had a minor anomaly near 1,365° K, with a heat absorption of 150 cal/mole. The heat content results are presented in both tabular form (at 100° intervals) and in algebraic form. Entropy increments, corresponding to the tabulated heat content results, also are listed.

Jan 1, 1963

By D. L. Albright, R. W. Kraft, J. A. Ford

HE unidirectional solidification of A1-CuAl, eutec-tic specimens to produce an essentially parallel lamellar structure has been described previously.' Ingots solidified in this manner ordinarily exhibit three macroscopic zones. In Zone I, at the head end of the ingot, a large number of slightly elongated grains occur in which the lamellae are highly distorted and twisted. After a few centimeters of growth, this distribution gradually changes to a small number of coarse grains elongated in the growth direction and in which the lamellae are quite regular, Zone 11. Zone 111, at the tail end of the ingot,

Jan 1, 1963

By John L. Miller

The synthetic fluormicas may be divided on the basis of silicon content into tetrasilicic, trisilicic, and disilicic. Properties of lead and barium disilicic fluormicas were determined to characterize these two representative members of the disilicic group. Properties described include unit-cell parameters from X-ray diffraction, optical data, chemical composition, density, melting point, and mechanical and dielectric properties. Both the lead and the barium micas were typically monoclinic; neither was sufficiently cleavable to yield usable mica splittings. Both yielded polycrystalline, machinable ceramics with excellent mechanical and dielectric properties.

Jan 1, 1963

By W. T. Benson

The nickel-bearing laterite deposits in the Pine Flat and Diamond Flat areas, Del Norte County, Calif., were investigated by the Bureau of Mines to determine the extent and nickel content of the two deposits and the amenability of the ores to metallurgical treatment. The work was based on drill-hole sampling and metallurgical tests in which attrition scrubbing and sizing, reduction roasting, and magnetic separation were used. Results of the sampling indicated that the deposits are comparatively small and are marginal or submarginal in grade. Metallurgical tests showed that no separation of cobalt from nickel and iron was made by sizing; however, a large portion of the chromium was separated. Reduction roasting and magnetic separation did result in upgrading the iron, nickel, and cobalt, and the simultaneous rejection of chromium.

Jan 1, 1963

By H. C. Carpenter

This literature study of methods for desulfurizing residual fuel oil was conducted by the Bureau of Mines at the request of the Department of Health, Education, and Welfare. The sulfur compounds in residual fuels are believed to consist chiefly of condensed thiophenes and other polycyclic sulfur compounds. Hydrodesulfurization appears to be the most promising method for desulfurizing these oils and is the only method applicable to all types of sulfur compounds. There are indications in the literature that hydrodesulfurization without hydrocracking of residual oils may require higher pressures than used in present desulfurization processes, but no cost data and little experimental data are available on the higher pressure operation. Literature proposals for hydrogenating residual oils and heavy crude oils are exclusively for hydrocracking the oils to lower boiling products with accompanying partial desulfurization of the residual fuel fraction. Costs of the hydrocracking operations appear the closest available to probable costs of hydrodesulfurizing the oils, and have been reported (in 1955 to 1957) as $500 to $840 investment cost per daily barrel of capacity, with total operating costs of 70 cents to $1.10 per barrel.

Jan 1, 1963

Albert M. Keenan, President, Thompson Creek Coal and Coke Corporation, Denver, Colorado, opened the third session of the Fifty-ninth Regular Meeting of the Rocky Mountain Coal Mining Institute at 9:30 a.m., and introduced the first speaker of the morning. Raphael J. Moses, Attorney, Colorado Water Conservation Board, Boulder, Colorado, spoke on "The Opportunity for Coal in Colorado River Basin Development." (For the printed text of Mr. Moses' paper see index.) Stephen F. Dunn, President, National Coal Association, Washington, D. C., was introduced by Mr. Keenan, and he addressed the Institute concerning "Coal and the Washington Scene."

Jan 1, 1963

By O. P. Arora, M. Metzger

Single-phase aluminum containing 1 to 600ppm copper was studied in 7 to 26 pct HCl. The corrosion rate in the autocatalytic stage was resolved into a constant intrinsic component and an acdelerating autocatalytic component, and attention was focused on the part of this stage where the corrosion rate could be described by a simple empirical relation. Autocatalytic corrosion in this period was localized and its rate increased rapidly with copper content and with the strength and chlaride content of the acid. The effects of adding cupric ion to 16 pct HCI were functionally and quantitatively inconsistent with the autocatalytic rates observed. A theory of these rates was given based on the deposition in nzetallic contact with the aluminum of part of the copper introduced by corrosion. It has long been known in a general way that aluminum containing sufficient copper suffers in hydrochloric acid an autocatalytic acceleration of corrosion resulting from the introduction into the acid of copper ions and their reduction on the specimen as elemental copper, which provides cathodes of low hydrogen overvoltage.'-3 In a previous paper, this phenomenon was identified in single-phase high-purity material at copper levels as low as 20 ppm and an empirical equation describing autocatalytic corrosion rates in 16 and 20 pct HC1 was presented. In the present work the range of acid strength and chemistry studied was extended, a more accurate empirical equation for the autocatalytic rate was determined, and a theory of this rate was formulated. A major source of interest in this system is the intergranular corrosion, which is also strongly influenced by copper content,= and an objective of the present work on general corrosion was to provide a basis for studying the role of copper content in intergranular corrosion, which is experimentally much less accessible.

Jan 1, 1963

By R. H. Richman

Coarse-grained Fe-Ni-C martensites formed at subzero temperatures were strained in compression at room temperature and the plastic deformation modes examined as a funclion of carbon content. At very low carbon levels, defovmation occurs hy wavy slip; commencing at about 0.05 pct C, mechanical twinning accounts for an increasing proportion of the plastic flow. Beyond approximately 0.4 pct C the deformation appears to be entirely by mechanical twinning. The habit planes of the operative twin modes were determined to be (113), (0131, and "(089)" in decreasing frequency of occurrence. Some of the implicaticms of Ihe o6served deformation modes upon the structure and properties of ferrous martensites are discussed. METALLURGISTS have long sought to explain the mechanical properties of ferrous martensites, particularly the extraordinary hardness and strength of the high-carbon varieties. Until recently the lack of precise knowledge of the structure of martensite crystals was the most serious barrier to understanding; however, the advent of thin-foil techniques for transmission electron microscopy has removed much of the mystery from martensite structure. Observations by Kelly and Nutting,"' and many others since, indicate that Fe-C based martensite crystals are internally twinned to a degree dependent upon the carbon content, and that a martensite plate containing 0.8 wt pct C or more consists of a stack of twin-related lamellae with each lamella on the order of l00A thick. Such a structure would be expected to influence greatly all aspects of metallurgical behavior, and many of the properties of Fe-C based martensites have been rationalized accordingly. Recent independent experiments led Winchell and cohen3 to conclude that the strength of ferrous martensite is derived primarily from solid solution hardening of the iron lattice by interstitial carbon atoms. Strength contributions from precipitation, dislocation-atmosphere interactions, clustering, short-range order, crystallite size, and so forth, were considered to be of secondary importance. In the view of Winchell and Cohen, the twinned structure of martensite serves mainly to limit the effective length of dislocation lines in the lattice, and thereby confers an added measure of hardening. Few properties of metallic crystals are as sensitive to metallurgical structure as are deformation mechanisms. It is somewhat surprising therefore, that, except for metallographic evidence of mechanical twins in strained martensite,4 no systematic examination of plastic deformation

Jan 1, 1963

By L. C. Brown, J. S. Kirkaldy

AS part of a program to investigate the diffusive properties of dilute ternary austenites, we have made a determination of the effects of cobalt on the activity of carbon in y iron. Samples of pure iron and Fe-Co alloys were equilibrated at 1000°C in controlled CO-C02 atmospheres, following the procedure of R. P. smith.' The 0.010-in.-thick samples were analyzed for carbon by microcombustion analysis2 to give a set of isoactivity curves. The latter were converted to activity-coefficient (standard state at infinite dilution) plots by combination with Smith's data' for the activity of carbon in pure iron measured in a CO-C02 mixture. Table I shows the composition of the base alloys used, while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In the notation of Wagner,' the interaction parameter is the second coefficient on the right, Eq. [I] adequately correlates the experimental points for those alloys which were prepared from electrolytic iron by arc-melting (2,4, and 7 pct Co). The results for the 10 pct Co alloy (supplied by Crucible Steel Co.) do not correlate with the others. In fact, the experimental points for this alloy correspond to an interaction parameter of It is possible that the interaction parameter is a function of concentration for large cobalt additions, but we are inclined to attribute the discrepancy to the presence of a significant amount of aluminum added to this alloy for deoxidation purposes (Table I). Preliminary measurements for the system Fe-C-A1 have indicated an interaction parameter of Which implies that the effect of aluminum in solution on the carbon activity is sixty times greater than the effect of an equal weight percentage of cobalt. These observations cast some doubt on the precision of the results of Chandhok, Hirth, and Dulis who used this same 10 pct alloy for their experiments, obtaining an interaction parameter of E = 2.2. There is considerable doubt as to the activity of a plane Fe-C system. Using a CH4-Ha mixture, Smith obtains cg = 6.1 for the effect of carbon on the activity of carbon in austenite, rather than the value of 8.9 given in Eq. [I]. The use of CHa-Ha mixtures has recently been questioned by Kaufman, Radcliff, and cohens who state that there is some possibility that other hydrocarbons are formed. Fortunately, the determination of the interaction parameter is not sensitive to the coefficient of Nc. For example, using the CHI-H2 results we obtain a value which is almost the same as that obtained using the CO-CO, results. The authors wish to thank Mr. E. J. Dulis of the Crucible Steel Co. of America for supplying us with samples of the 10 pct Co alloy used in their original work. Financial assistance from the American Iron and Steel Institute is gratefully acknowledged.

Jan 1, 1963

By K. G. Kreider, J. H. Brophy, J. Wulff

The technology of nickel-activated sintering of tungsten powder has been successfully applied to the densification of plasma-sprayed tungsten. Nickel was added by infiltration in a zinc solution followed by evaporation of the solvent. After sintering one hour at 1300°C density 95 pct of theoretical and transverse rupture strength of 74,000 psi were obtained. Shrinkage was found to be anisotropic and the mechanism of densification was comparable to that found in the nickel-activated sintering of tungsten powder. 1 HE use of a plasma spray gun for the fabrication of massive tungsten parts has become increasingly interesting. Applications now exist where a deposit in the as-sprayed condition is satisfactory. However, these deposits are generally characterized by a lamellar anisotropic microstructure containing 15 pct porosity of which, typically, two-thirds is open to the surface. Mechanically, the as-sprayed deposits fail at relatively low stress levels with a biscuit-like fracture. As a result of these problems the possibility of improving structure and strength by sintering treatments subsequent to spraying is particularly attractive. Preferably this sintering treatment should be adaptable to large bodies of sprayed metal. The similarity between the as-sprayed tungsten structure and that of a powder compact suggests that the relatively low-temperature activated sintering technique1 might be profitably employed in the densification of plasma-sprayed tungsten. It was the purpose of the present investigation to develop a technique for introducing the nickel-activating agent into the sprayed structure, to evaluate the amount and mechanism of densification obtained as a function of time and temperature, and to obtain an indication of the relative strength before and after sintering. EXPERIMENTAL PROCEDURE Powder used for spraying was purchased from the Wah Chang Corp. in several size fractions ranging from an average size of 4 to 150 . These powders were sized further for an explicit study of the influence of average feed size on densification. All powders were dried at 200°C before use. Spraying was accomplished with a Plasma Flame unit manufactured by Thermal Dynamics Corp. Several modifications of the unit were helpful in conducting the investigation. A variable speed auger feed mechanism coupled with the carrier gas mecha nism facilitated the use of fine particle sizes. A coil of ten turns of copper tubing in series with the arc power and concentrically would around the nozzle improved nozzle life and extended the range of operating currents available. The function of the auxiliary coil was to cause the arc to spin and to prevent impingement at only one point in the nozzle. Normally air sprayed deposits were made with an arc maintained at 400 amp at 50 to 70 v. The arc was blown by a gas mixture containing from 5 pct H, 95 pct N for the finest powder feed sizes ranging to 20 pct H, 80 pct N for the coarsest size. The flow rate was maintained at 100 cu ft per hr NTP through a nozzle of 0.25 in. ID. When apraying in air, the powder stream was directed toward an aluminum substrate for ease of mechanical removal of the deposit. The substrate was cooled by diverting the plasma flame with an air jet, and a second jet was directed on the deposit surface. In this configuration a gun-to-work distance of 2 to 3 in. was found to be satisfactory. Fig. 1 represents a typical as-sprayed deposit micro-structure. Laboratory studies of protective atmosphere spraying were carried out in cylindrical chamber 8 in. in diam by 18 in. in length. In operating the nozzle attached to such a chamber, particular care was required to avoid nozzle burn out due to reduced gas flow. The structure and density of the chamber sprayed deposits varied over wide ranges depending on substrate temperature. For the purposes of this investigation, flat deposits were made approximately 2 in. sq by 3/8 in. thick. From these deposits individual samples were cut an ground to a rectangular shape typically 1 1/2 in. by 1/8 in. sq such that the long dimension was perpendicular to the spraying direction. For the study of shrinkage anisotropy deposits up to one inch thick were produced. From these, rectangular samples were cut having a longer dimension parallel to the spraying axis. Prior to the addition of activating agent, the samples were deoxidized in hydrogen at 800°C for 20 min. No detectable dimensional or microstructural change was observed after this treatment. The addition of nickel was accomplished by infil-

Jan 1, 1963