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By John P. Harmon

Vehicles traveling on untreated dirt and gravel roads at open-pit mines disseminate high concentrations of dust (fig. 1). Excessive dust creates safety hazards by reducing visibility and may endanger the health of the men who breathe it. If the dust contains free silica, it can cause silicosis. In addition, maintenance costs of mechanical equipment are increased if equipment is operated in extremely dusty places. Dust on haulage roads in hot, arid country can be controlled if the surface of the road is sprinkled frequently and adequately with water. Often, when roads are sprinkled with water to control the dust, hazards are caused through reduced traction and skidding because of the mud that is formed on the surface of the road. Reducing the amount of water used will help to reduce the hazard of skidding.

Jan 1, 1957

By R. Maddin, N. Ujiiye

ALTHOUGH the cold-rolled texture for body-centered-cubic metals and alloys is well known (see, e.g., Barrett'), the pole figure representing the texture may be interpreted in two ways. It may be regarded as consisting of several ideal preferred orientations with an associated spread (a view which is shared among several investigators2), or it may be regarded as consisting of two sets of continuous preferred orientation also with an associated spread."." Recently, Chen and Maddin7 noted a stable (001) [loo] end orientation for molybdenum single crystals rolled at low rates of reduction provided the initial rolling. orientation" was close to the cube ori-

Jan 1, 1957

By G. W. Govier

Measurements of the settling rates and the rheological behaviour of heavy media formed of fine suspensions in water of each of magnetite, ferrosilicon, and galena have been made. For media ranging from 1.6 to 2.8 specific gravity the settling measurements gave initial settling rates of from 0.5 to 0.01 ?cm. 'Per minute for magnetite; from 4.0 to 0.8 cm. per minute for galena; and from 35 to 1.6 cm. 'Per minute for ferrosilicon. These measurements indicate the ?relative stability of the suspensions and should be helpful in establishing the useful specific gravity range for each medium. Measurements of the consistency of the media were made with a Fann Model 35 rotational viscometer. Aibnormal or non-Newtonian behaviour was observed in the case of each media, the apparent viscosity being dependent upon the rate of shear or the intensity of motion. Measurements were made over the rate of shear range of 10? to 1,000 reciprocal seconds. The apparent viscosities of the magnetite media ranged from 450 down to 4?0 centipoise at 2.30 specific gravity, and from 2,450 down to 700 centipoise at 2.80 specific gravity. In the case of the galena media, the variation was from 40, through a minimum of 6, to 10 centipoise at 2.20 specific gravity, and from 950, through a minimum of 180, to 450 centipoise at 3.6 specific gravity. The ferrosilicon suspensions exhibited apparent viscosities ranging from 42, through a minimum of 5.6, to 9 centipoise at 1.9 specific gravity, and from 160, though a minimum of 35, to 85 centipoise at 2.8 specific gravity. The dependency of apparent viscosity or consistency upon intensity of motion is considered to be of particular significance in applications of heavy media where the medium is in rapid motion.

Jan 1, 1957

By Donald Jaffe, Michael B. Bever

The solidification of Al-Zn alloys (2 to 70 pct Zn was investigated at different rates of solidification. The resulting structures were studied; the amounts of nonequilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography after activation of the zinc by neutron irradiation. These compositions were also determined from microhardness values. IN a recent investigation of the soltdification of aluminum-rich AI-Cu alloys,' the amounts of non-equilibrium eutectic were measured and compared with the amounts calculated on the assumption of no diffusion in the solid. The compositions of the cored primary constituent were investigated by quantitative autoradiography. The work reported here extends the investigation of nonequilibrium solidification to the Al-Zn system in the range from 2 to 70 pct Zn. In addition to autoradiography, microhard-ness values were used to determine compositions on a micro scale. Solidification Experiments The alloys contained approximately 2. 6, 12, 20, 30, 50, and 70 wt pct Zn and the balance aluminum. According to published diagrams the eutectic reaction occurs at 382°C between the eutectic liquid (95 pct Zn), a (82.8 pet Zn), and $ 498.9 pct Zn). Solid-state reactions at lower temperatures (due to the miscibility gap between 350" and 275"C, the eutectoid at 275'C, and the precipitation from supcrsaturated a) did not affect this investigation. Even if they occurred to any appreciable extent, they did not alter the evidence pertaining to the solidification structures. The alloys had to be of high purity to avoid radioact~ve contamination during activation. The aluminum analyzed 0.015 pct Si, 0.009 pct Fe, less than 0.004 pct Cu, and less than 0.006 pct Mg with traces of sodium and titanium; the zinc was reported to be at least 99.99 pct pure with traces of iron and magnesium. The alloys were prepared under argon in an induction-heated, bottom-pouring furnace, and poured into a coated steel mold, which could be preheated to temperatures up to 700°C in order to control the rate of solidification. The pouring temperatures ranged from about 40" above the liquidus for 2 pct Zn alloys to about 130°C above the liquidus for 70 pct Zn alloys. As soon as the melt entered the mold, the readings of a thermocouple placed % in. above the bottom of the mold were recorded by a recording potentiometer. Cooling at the rate induced by the initial temperature of the mold was continued to a temperature 100°C below the liquidus; the mold with its contents was then quenched in icy brine. Quenching from a fixed interval below the liquidus was used to provide a standardized procedure, since the solidus and liquidus temperatures and the interval between them vary greatly over the composition range investigated. The temperatures from which the samples were quenched were below the equilibrium solidus, but under nonequilibrium conditions some liquid was still present. This residual liquid solidified during the quench. The samples measured 314 in. diam and 11, in. height. Drillings for chemical analysis were taken

Jan 1, 1957

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By K. T. Aust

The relative interfacial energies of symmetrical tilt boundaries in silver of greater than 99.999 pct purity were measured as a function of orientation difference 0 between 9° and 36° about <001>. The results are in good agreement with the dislocation model of the grain boundary. The energy vs H curve may be represented by the Shockley and Read equation in the form Eoe (0.55—In 8). READ&apos; has indicated that an ideal experimental method of testing the predictions of the dislocation theory of the grain boundary would be to measure the interfacial energies of symmetrical tilt boundaries between face-centered-cubic grains that have a common <001> axis, as a function of orientation difference 0. The misfit H should be defined by a rotation of each grain through an angle of H/2 away from the boundary. Such boundaries might be expected, from geometrical considerations, to be made up of a series of edge dislocations, at least for small values of 0. Energy vs H relationships for tin&apos; and lead:&apos; were previously obtained for an asymmetrical tilt boundary separating two grains in which generally only one grain was rotated about a <001> specimen axis through an angle of H away from the boundary, the other grain remaining fixed. It is possible, however, that the boundary atoms in tin and lead may have attained a symmetrical position, in relation to the orientations of the grains on either side of the boundary, during equilibrium annealing. The two sets of measurements on silicon ferrite&apos; were somewhat better suited for comparison with theory, since the boundaries were symmetrical tilt boundaries in which the axis of relative rotation was <110> in the first series and <l00> in the second; but this alloy has a body-centered-cubic structure. Although the grain boundaries in silver" were symmetrically tilted, the axis of relative rotation was not a simple crystallographic direction, and it varied from boundary to boundary. Although the above measurements were in good agreement with the Shockley and Read equation,"&apos;: it appeared desirable to carry out experiments under the ideal conditions specified by Read.&apos; Consequently, the relative energies of symmetrical tilt boundaries in silver between grains that have a common <001> axis were measured. The technique of equilibrating grain boundaries in oriented tricrystals was used rather than the less satisfactory thermal groove method previously employed for silver bicrystals." Experimental Details and Observations The solidification and seeding techniques, described previouslyh for growing tricrystals of controlled orientations, were used to prepare tricrystal specimens from silver of greater than 99.999 pct purity. The silver was obtained from American Platinum Works, Newark, N. J., in the form of poly crystalline rods 10 cm long and 7 mm in diam. These rods were then cold worked by rolling or drawing them into suitably shaped blanks. Single crystal seeds and tricrystals were grown in a high purity graphite boat by means of a movable furnace with globar heating elements. The graphite boat was enclosed in a Vycor tube, which was first evacuated to about l00/u Hg and then filled with a static argon atmosphere. The maximum temperature outside the Vycor tube was 1250°C. A typical tricrystal specimen of silver is shown in Fig. 1. Grains B and C were grown from seed crystals with a <001> specimen axis or longitudinal direction parallel to the direction of growth and with another <001> direction perpendicular to the surface. Each of the two seed crystals was rotated 18" about the <001> specimen axis but in opposite directions away from the boundary. A symmetrical tilt boundary, therefore, separated grains B and C with an orientation difference 8 of 36" about <001>. Grain A in Fig. 1 was grown from the middle seed with a <110> direction parallel to the specimen axis and with a <001> direction inclined at 45&apos; to the surface of the specimen. The interfaces sepa-

Jan 1, 1957

By J. E. Rowland

NIOCALITE is a new mineral species which has been identified in rock from the Oka district, Quebec. It occurs as prismatic crystals up to l 0 mm. in length and I mm. in width, in coarse, white, crystalline calcite with associated apatite, diopside, biotite, pyrochlore, and niobian perovskite. The crystals of niocalite are light yellow in col-our and have a vitreous lustre. The optical properties of niocalite (I) are as follows: Biaxial negative -2V = 56° a = 1.700, [ ] = 1.730 Birefringence y -a = 0.030 Optic orientation: X = b, Z/\c 12°, Y , /\a = 32° The specific gravity is 3.32 and the hardness is approximately 6 (Mohs scale). A detailed analysis performed on 2.4 gm. of hand-picked material reveals that niocalite is essentially a calcium niobium silicate. Table I gives the result of the analysis. Crystals of niocalite, apparently suitable for X-ray diffraction work, were selected, and single crystal photographs were obtained using both Weissenberg and Precession cameras. Initial difficulties were encountered in interpreting these films, and in correlating the crystal data with the optical data. The in-consistencies were explained by the fact that every grain examined was twinned to some extent.

Jan 1, 1957

By C. H. Schack

Although viscosity is known to be important in processing and handling finely ground urea, its effect has never been fully quantified. This report describes the methods used and the results obtained in the initial phases of a broad investigation of the influence of viscosity of water suspensions of minerals in flotation, thickening, filtering, and other mineral-dressing unit operations. Several types of vis-cosimeters were tested before reliable and reproducible results could be obtained on mineral suspensions. After the viscosimeter used in the research was calibrated and standardized, tests were made on six pure minerals to study the relationship of pulp density, particle size, crystallinity, and cleavage on viscosity. An orifice-type viscosimeter equipped with a mechanical stirrer gave as good results as other types and was more flexible, faster, and simpler to operate. The orifice-type viscosimeter, when calibrated and standardized with glycerin and water mixtures, proved satisfactory over a wide range of viscosities. The accuracy and reproducibility were reasonably constant between 1 centipoise and 200 centipoises, the anticipated range in common mineral-dressing unit operations.

Jan 1, 1957

Jan 1, 1957

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

Jan 1, 1957

By Gerhard Bockstiegel

Kuczynski&apos;s formula has been derived for the case of nonspherical particles. TWO formulae of Kuczynski&apos;s type have been derived, one describing the increase in tensile strength, the other describing the progress of shrinkage of a powder compact. It has been strength,shown that the exponents of all three formulae each contain two magnitudes of different physical characters, viz, the geometrical factor a and the kinetic factor ß. The interrelationships between the three exponents are stated. SOME years ago Kuczynski1 experimentally showed that the radius, x, of the area of contact between very small spherical metal particles and a metallic block is related to the time of sintering, t, by the following equation x = constant tk [11 where k has the value 1/5 or 1/7. Assuming that the metal particles were perfect spheres and the metallic block was perfectly flat, he derived the foregoing equation from theoretical considerations of the process of material transport in metals, and he showed that exponent k is different for different mechanisms of transport, e.g., k = 1/2 for viscous flow (according to Frenkel2), k = 1/3 for evaporation and condensation, k = 1/5 for volume diffusion, and k = 1/7 for surface diffusion. From this Kuczynski concluded that the mechanism of transport was either volume diffusion or surface diffusion, depending on whether the value of k, as found in his experiments, was 1/5 or 1/7. Subsequently. Cabrera8 corrected Kuczynski&apos;s calculations with regard to surface diffusion, showing that the theoretical value of exponent k is 1/5 for both volume and surface diffusion. He supposed that the different experimental values of k were due to slight differences in the shape of the metal particles. An exponential relationship similar to the aforementioned was found by Okamura, Masuda, and Kikuta,4 Masuda and Kikuta, and Takasaki8 when studying the rate of shrinkage on powder compacts during sintering. The authors measured the shrinkage by means of the fraction w = Vp — V./Vp — V,,,, where V,, is the volume of the green compact, V, is the volume of the sintered compact, and V,,, is the volume of the compact in its densest state. This fraction, w, they found, is related to the time of sintering, t, by the equation w == constant tm. [21 Further, Bockstiegel, Masing, and Zapf7 observed that the tensile strength, s, of sintering iron powder compacts can also be related to the time of sintering, t, by an equation of the foregoing type, i.e., s = constant tn. [3] For exponent n the values 0.28 (S=2/7) and 0.35 ( 2/5) were obtained, and the authors pointed out that there might exist a simple interrelation between exponent n as found in their experiments and exponent k in Kuczynski&apos;s equation. The authors supposed that 2k = n, since the strength of adhesion between a metal sphere and a block (as in Kuczyn-ski&apos;s experiments) must approximately be proportional to their contact area, p. x2. Theoretical Considerations This paper is an attempt to correlate the fundamental experiments of Kuczynski&apos;s type with the results obtained with powder compacts as represented by Egs. 2 and 3. In particular, the paper is to show how the rate of sintering is influenced by the geometry of the sintering particles and by the type of material transport. As the geometry of particles conglomerating in a powder compact is very complex, some simplifying assumption has to be made, of course, in order to adapt the problem to mathematical treatment. In the following paragraph a suitable simplification is introduced, and Kuczynski&apos;s formula is derived for the case of nonsphcrical particles. Relation Between Area of Contact and Sintering Time—As the face of contact between two particles in a sintering powder compact is not necessarily a circle (as in the case of spheres sintering to a block), Kuczynski&apos;s formula is modified as follows: Let the perimeter of the face of contact be described by means of polar coordinates R, 4, as shown in Fig. la, so the area of contact, f, is determined by f= 1/2 . S112p[R(Æ) ]2 dÆ [4] Then, let the two particles be intersected by a plane perpendicular to area f. The intersection is shown in Fig. lb. According to the nomenclature in this figure, the distance, h, between the surfaces of the two particles is a function of T and Æ: h = h(r,Æ). For the particular case of spherical particles, as in Kuczynski&apos;s theory, this function becomes: h = constant r2. It shall be assumed here that in the close neighborhood of their

Jan 1, 1957

By Ford R. Bryan, Edward F. Runge

BECAUSE of the need for ductile heat resistant alloys of non-strategic composition, there has been metallurgical development of Fe-A1 alloys possessing improved ductility and hot strength, together with high oxidation resistance. Iron and alu- minum form solid solutions up to approximately 35 pct Al. Alloys in the 8 to 12 pct A1 range are characterized by excellent oxidation resistance, high electrical resistivity&apos; and, when appropriately alloyed, have creep rupture strength equivalent to that of the austenitic stainless steels.&apos; At higher aluminum levels, the magnetic properties are of considerable interest. Nachman and Buehler" have recently reported on the desirable magnetic characteristics of the 16 pct alloy.

Jan 1, 1957

By M. T. Simnad, G. Derge, Ling Yang

A method is described for using radioactive tracer for the direct determination of ionic mobility in a molten electrolyte. The ionic mobility of Fe" in silica-saturated iron silicate is found to be 0.0009 (*0.0002) cm2 sec &apos; volt L at 1250°C. eLECTROCHEMICAL studies&apos;, &apos; of molten iron eE oxide and iron silicates have shown some ionic conductivity at all compositions. The current efficiency in electrolysis increases with the concentration of silica to a maximum of 90 pct at about 34 pet SiO,. In the silica-saturated melts the transport number of ferrous ions is near unity, indicating that

Jan 1, 1957

By W. A. Cole

The sulfur shortage that existed during the Korean conflict stimulated interest in coal measures as possible sources of sulfur. One of the areas brought to the attention of the Bureau of Mines was in Marion County, Iowa, where comparatively high-sulfur coals and other marcasite-bearing strata were known to occur. A Bureau of Mines engineer inspected the marcasite occurrence on December 4, 1954; this prompted further work on the Iowa coals and associated formations as a source of iron sulfides. An investigation of the Iowa high-sulfur coals was undertaken including core drilling, field reconnaissance, and compilation of data pertinent to consideration of the following: 1. Upgrading Iowa coal by mechanical cleaning and the feasibility of recovering sulfur from coal brasses. 2. Possibility of processing the high-sulfur coals by adaptation of methods employed in processing industrial gases to produce sulfur and sulfur products. 3. Possibility of finding concentrations of iron sulfides in associated rock formations in sufficient quantity for economical recovery.

Jan 1, 1957

By A. U. Seybolt, R. A. Oriani

The pressure and composition of the solid solution of nitrogen in chromium has been investigated as a function of temperature. The partial molal heat of solution, the activity of nitrogen in solid solution, and the partial molal free energy have been computed. The enthalpy of three reactions is summarized: N + 2Cr(3) = Cr2N(4), H° = —28,500 cal per mol 1/2N2(p) + 2Cr(8) = Cr2N(3)1 ?HO = —23,500 cal per mol 1/2N2(p) = N, ?H° = 5,000 cal per mol. WORKERS who have investigated the problem of the preparation of ductile chromium have been concerned with the effects of minor amounts of impurities upon this refractory metal. In particular, gaseous impurities such as oxygen and nitrogen have been suspected of causing trouble because of many known cases where brittleness in transition elements has been definitely traced to these elements. In order to evaluate the possible effects of the nitrogen impurity in chromium, it appeared desirable to learn something of the dependence of the nitrogen solubility upon temperature and pressure. Previous Work Maier3 in 1942 in his treatise on sponge chromium reviewed the thermodynamics of the chromium nitrides Cr2N and CrN, both of which are well-estab- lished compounds, but which apparently have not been studied in much detail. Maier presented some free energy-temperature expressions for the reactions 2 Cr,N = 4 Cr + N2 [1] and 4 CrN = 2Cr2N + N2 PI based mainly on the work of Satoh2 and Sano." Pearson and Ende3 in 1953 briefly reviewed the thermodynamics of Cr-N using the same data available to Maier, and also derived a free energy-temperature expression for reaction 1. Of the two nitrides mentioned previously, the present investigation was only concerned with Cr,N, since this nitride is in equilibrium with the metal phase, at least over most of the temperature range, Blix4 in 1929 established the structure of Cr2N (close-packed-hexagonal) by X-ray diffraction methods, and indicated that its homogeneity limits extend from 11.2 pet to 15.1 wt pet N. At a temperature of 1200°C, 38 mm Hg from the Maier expression and 43 mm Hg from the Pearson

Jan 1, 1957

By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By J. Gordon Parr, D. H. Polonis

IN a previous study of hypereutectoid Ti-Ni alloys&apos; a substructure was observed in quenched powder specimens when the constitution was 100 pet retained ß body-centered-cubic phase. The alloy powders were quenched from 1000°C by a blast of helium gas and precautions already described were observed throughout the work, to minimize contamination. Ogden et al.2 have previously observed subboundaries in the ß phase of a Ti-Mn-N alloy; but this structure was attributed to nitrogen-rich a precipitation. The nitrogen content of the Ti-Ni alloys does not exceed 0.02 pet and the quenching rate was sufficiently rapid to suppress precipitation reactions. Since X-ray diffraction results have confirmed the absence of any second phase which might account for this phenomenon, it seems unlikely that this substructure is explicable in terms of nitrogen content. Fig. 1 shows the substructure in adjacent grains of 100 pet ß phase in a quenched 6 atomic pet Ni alloy. Fig. 2 shows adjacent ß grains in a similarly treated alloy; one grain contains marked intracrys-talline boundaries and the other is completely free from any substructure. The suberystals appear to have fairly regular shapes, suggesting a regular orientation relationship among them. Tempering the retained ß structure at temperatures below the eutectoid eliminates the substructure at an early stage of ß decomposition. At the present time it is possible only to guess at an explanation for this subboundary phenomenon, since very little work has been reported on substructures resulting from phase changes. It is believed that the present phenomenon is due to poly-gonization resulting from unrelieved stresses set up

Jan 1, 1957

By L. O. Bacon

IN the spring of 1952 Calumet and Hecla Inc. began a geophysical program near Shullsburg, Wis., in the Wisconsin-Illinois lead-zinc district, to assist the geological and drilling exploration programs. Sphalerite, the ore mineral in this area, occurs with a considerable amount of marcasite. In general the higher the percentage of sphalerite in the ore, the higher the percentage of marcasite; however, there may be mineralized zones high in marcasite but low in sphalerite. Orebodies in general are relatively narrow and elongated. Reconnaissance exploration of virgin areas consisted of drilling along lines at 500 to 1000-ft intervals. Whenever a mineralized zone was intersected additional drilling was done to determine whether or not the zone carried zinc percentages of ore grade and, if so, to delineate the body. Calumet and Hecla Inc. was interested particularly in a method that would show the direction and position in which to drill from the original discovery hole. This suggested a method of contacting the orebody, which occurs at depths ranging from 100 to 200 ft, with one electrode. After a number of procedures had been considered it was decided to use equipotential line methods. Instrumentation and Field Procedure: The power source used was a 400-cycle Signal Corps motor-generator having a rated output of 1200 w at 115 v. The detection unit consisted of test probes, a two-stage amplifier, and &apos;head phones for determining the equipotential line by audio null. Field procedure consisted of contacting the sulfide body in the hole by a specially built spring-loaded expanding electrode which would be lowered into the hole, in the closed. position, until it reached the mineralized zone. At that point the mechanism was released so that the arms would make contact with the walls of the hole in the same manner that a well-bore caliper does. This electrode was then connected to the generator, the other terminal of which was connected to the surface electrode. The surface electrode was either a point, a straight line, or a circular line electrode. The point surface electrode was placed at a considerable distance from the hole, that is, 2500 to 5000 ft, depending somewhat upon the depth to the sulfide zone and the distance from the hole containing the subsurface electrode to which exploration was considered. A higher voltage output from the power source would have been desirable, although no difficulty was encountered in determining null points to a distance of 500 ft. Straight line electrodes used were approximately 1000 ft in length at a distance of approximately 1000 ft from the hole containing the subsurface electrode. The circular line electrode used consisted of 4400 ft of bare No. 10 copper wire, which provided a circle of 700-ft radius. All line electrodes were fastened to the ground at 20-ft intervals with copper staples 4 in. long. Equipotential points were determined at 25 to 100-ft intervals. Location of the points was made by plane table and stadia. In open country with a three-man crew, the points were plotted as they were determined. With a two-man crew, pegs were placed at equal potential points and surveyed in after several equipotential lines were determined. Although interpretation of results given in this paper is qualitative, the paper as a whole would not be complete without a discussion of the theoretical distribution of potential due to a circular line electrode. The theoretical distribution would be required if a quantitative interpretation of the measured potential distribution were to be made. The theoretical potential distribution due to a circular line electrode can be obtained by means of Legendre polynomials. Using the method as developed by Weber,&apos; the potential for a circular line electrode in a semi-infinite, homogeneous, isotropic medium can be expressed, using the spherical coordinate system, as: V(r,n) = pi/2pR[S(r/R)nPn(cos?)Pn(cosa)]r<R [1] er V(r,a) =pI/2pr[S(r/R)Pn(cos?) Pn(cosa)]r>R [2] where: 0 is the angle at the origin, taken on the axis of the circular electrode between the axis and the line drawn to the circumference of the circular electrode. a is the angle between the axis and the radius, r.

Jan 1, 1957

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957