Search Documents

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

By L. R. Page, J. J. Norton

EFFECTIVE methods for determining grade and reserves of pegmatites in advance of mining have been developed in recent years. When intensive work began on the economic geology of pegmatites during the early years of World War 11, it was widely believed that grade and reserves could be estimated only in a most general way. The literature indicated that not all pegmatite deposits are unpredictable, but statements emphasizing unpredictability and irregularity seem to have been more widely accepted. Many standard references reflect the prevailing opinion that minerals: are unsystematic in their occurrence in pegmatites. Pegmatites have been described as "notorious for their irregular structure," and minerals within pegmatites as "irregularly distributed." "irregularly disseminated," of "erratic occurrence," "proverbially erratic in distribution," "characterized by extreme irregularity in ... size and distribution of the essential minerals, and variety and proportion of the accessory minerals," and "spotty.&apos;"" Over many years, however, geologic techniques have been applied with increasing success to economic analysis of pegmatites. Investigations, chiefly since 1939, have shown that mineral distribution and structure of pegmatites are largely systematic and that detailed geologic study can be used to predict the size and shape of mineral deposits in pegmatites. Because the writers are most familiar with the pegmatites of the Black Hills, S. D., examples cited are from that area." Pegmatites mined in other dis- * All examples are described more cornpletely elsewhere.: tricts are similar to those in the Black Hills," and the techniques described here have been applied by geologists and engineers working in other districts. In actual practice few pegmatite mine operators attempt to make accurate estimates of grade and reserves in advance of mining. Many deposits are too small for mining except on a very small scale; few pegmatite mines have more than ten employes. Hence there is little systematic preparation for mining, and the capital outlay may be so small that only a general knowledge of reserves is necessary. Technical personnel are rarely employed by pegmatite mine operators to make such estimates. In the future, however, as capital outlay becomes larger, estimates of grade and reserves will have to be more accurate. Geologic Aspects of Determining Grade and Reserves Estimating grade and reserves requires that the type of pegmatite, the size and shape, and the internal structure be determined by detailed geologic mapping and careful mineralogic study. The wide variations in the texture and distribution of minerals within many pegmatite deposits make a thorough geologic study of this kind necessary before it is possible to decide what sampling methods should be used to determine mineral content or grade. Types of Pegmatites: The first step in economic appraisal of a pegmatite is to determine the min-eralogical and structural type. In general, pegmatites may be classified into two groups: 1) those in which component minerals are more or less evenly distributed throughout the entire body and show relatively minor variations in texture, and 2) those in which component minerals have been segregated into units with recognizable differences in texture, mineralogy. or both. Johnston" has classified these types of pegmatites as homogeneous and heterogeneous, respectively. Cameron et al.10 have used the terms ~inzoned and zoned for similar types. The difference between the homogeneous and heterogeneous types is of great commercial importance. Homogeneous pegmatites can seldom be mined where the products are concentrated by the hand methods now commonly used, but they have been mined in a few places where a milling process has

Jan 1, 1957

Jan 1, 1957

By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these&apos; the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert&apos;s law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957

By Benny J. Nelson

To obtain information on the effect of gallium upon the corrosion of magnesium alloys, tests were made on the commercial alloy AM52S (Mg-3 pct Al-1 pct Zn-0.2 pct Mn) and experimental

Jan 1, 1957

By T. S. Hutchinson, C. E. Kemp

The bottom water drive analysis presented by Muskat has been extended to include fields with wider well spacings. Curves are presented from which volumetric sweepout, water-oil ratio, and rate relations may be calculated. The effects of non-unity ratios on sweepout eficiency and productivity decline have been studied by an approximate method. Also, the effect of gravity on volumetric sweepout has been approximated for a particurlar geometry. INTRODUCTION The purpose of this paper is to report work done in applying the analysis of bottom water drive reservoirs given by Muskat1 to a larger class of reservoirs, to extend this analysis to include the effects of gravity and non-unity mobility ratios in an approximate manner, and to investigate the rate of decline of productive capacity. The bottom water drive type reservoir is one where the oil is underlain by a water zone of sufficient thickness that water movement is essentially vertical. This system is defined in more detail in the appendix and a one well element is shown diagrammatically in Fig. 1. Muskat obtained solutions to the equations describing the volumetric displacement efficiency of idealized bottom water drive systems by assuming that gravity effects due to differences in density betwecn oil and water were negligible and that the mobilities of oil and water were the same. If either of these assumptions is not made, the complexity of the system makes an analytical solution well nigh impossible at the present stage of mathematical development. Coles and Stade&apos; developed an approximation to consider these factors. The authors have refined approximations, starting with the same basic assumption, which should give a somewhat quantitative picture of bottom water drive performance when mobilities are not equal and the effects of gravity are not negligible. The results of these approximate calculations can then be used to obtain the decline in well productivity as the field is depleted.

Jan 1, 1957

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By David B. Burrows, Francis R. Conley

INTRODUCTION A prerequisite to the evaluation and management of oil properties is accurate information derived from the analysis of core samples; but reliable data, such as porosity and permeability, can result only if all oil and water have been removed from the core samples analyzed. The most common method of core cleaning used to date has been Soxhlet extraction—a somewhat static technique, which depends upon the slow diffusion of hot solvent through the core sample. Soxhlet extraction performs satisfactorily only with highly permeable samples and at best requires long cleaning periods. The centrifuge method was developed in 1951 by Continental Oil Co. to overcome the inefficiencies inherent in the Soxhlet method. The new method is basically an operation in which hot solvents are caused to flow through the samples under the influence of centrifugal force. The centrifuge unit has proved so successful that samples which formerly required days for partial extraction can now be completely cleaned in approximately one hour. The original idea was conceived in 1950 by Elmer S. Messer, whose early experiments consisted of flowing solvent over sandstone samples suspended in a revolving basket and driven by a vertically mounted vacuum cleaner motor. Results were so outstanding that more permanent units were constructed. A modified model using this basic design was recently built by Core Laboratories, Inc., and is now used regularly in their operations. DESIGN Fig. 1 shows a photograph of the two extractors routinely used to clean small core plugs in the Production Research Div. of Continental Oil Co.&apos;s Ponca City laboratories. For illustrative purposes, the basket from one of the units has been removed, and because both extrac- tors are of identical design only one is described in the following discussion. Each extractor unit consists of a centrifuge and a solvent still. The core basket of the centrifuge is made of mild cold rolled steel 7 1/2 in. in diameter and 1 1/8 in. deep. The basket holds 18 1-in. samples (cubical or cylindrical) and is attached directly to a cone fitted to the shaft of the motor. Both the outer rim and the hollow hub of the basket contain perforations for the passage of solvent and extract. The solvent is delivered to the perforations by means of a copper tube inserted into the hollow hub. The motor is a vertical tool post grinder motor; (115 v, 5.6 amp, 0-60 cycles, AC-DC, rated at 1/3 hp). It has a rated speed of 10,000 rpm under full load and 15,000 rpm with no load. Variation of speed is obtained by the use of a variable transformer. The solvent still was constructed from one end of a stainless steel oxygen bottle by inserting a heating element, sight glass, and piping as shown on the schematic diagram, Fig. 2. The heater used was a three-position, 1,000 w, 115-v, immersion type. Intermittent flow of solvent to the centrifuge is obtained by means of a siphon bottle inserted between the condenser and the centrifuge.

Jan 1, 1957

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500&apos; to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast&apos; reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By F. E. Werner, B. L. Averbach, Morris Cohen

THAT bainite formed near the M, temperature bears a striking r esemblance to martensite tempered at the same temperature has been shown by the electron microscope.&apos; By means of electron diffraction,&apos; it has been established that carbide and cementite are present in bainite formed at 500°F (260°C); these carbides are also found in martensite tempered at 500°F (260°C).&apos; The investigation reported here is concerned with an X-ray study of the matrix phases in lower bainite and tempered martensite. These phases have turned out to be dissimilar in structure; the matrix of bainite is body-centered-cubic while that of tempered martensite is body-centered-tetragonal. A vacuum-melted Fe-C alloy containing 1.43 pct C was studied. Specimens of 16 in. diam were sealed in evacuated silica tubing and austenitized at 2300°F (1260°C) for 24 hr. One specimen was quenched into a salt bath at 410°+7 °F (210°+4°C), held for 16 hr, and cooled to room temperature. The structure consisted of about 90 to 95 pct bainite, the re: mainder being martensite and retained austenite. A second specimen was quenched from the austen-itizing temperature into iced brine and then into liquid nitrogen. It consisted of about 90 pct martensite and 10 pct retained austenite. The latter specimen was tempered for 10 hr at 410°+2°F (210°+1°C). The specimens were then fractured along prior austenite grain boundaries (grain size about 2 mm diam) by light tapping with a hammer. Single aus-tenite grains, mostly transformed, were etched to about 0.5 mm diam and mounted in a Unicam single crystal goniometer, which allowed both rotation and oscillation of the sample. Lattice parameters were measured by the technique of Kurdjumov and Lyssak. This method takes advantage of the fact that martensite and lower bainite are related to austenite by the Kurdjumov-sachs orientation relationships Thus, the (002) and the (200) (020) reflections can be recorded separately, permitting the c and a parameters to be determined without interference from overlapping reflections. According to these findings, the matrix phase in bainite is body-centered-cubic and, within experimental error, has the same lattice parameter as ferrite (2.866A). On the other hand, martensite, tempered as above, retains some tetragonality, with a c/a ratio of 1.005t0.002. Most workers in the past have assumed that bainite is generated from austenite as a supersaturated phase, but the nature of this product has not been established. The question arises as to whether bainite initially has a tetragonal structure and then tempers to cubic, or if it forms directly as a cubic structure. If it forms with a tetragonal lattice, it might well be expected to temper to the cubic phase at about the same rate as tetragonal martensite. The martensitic specimen used here was given approximately the same tempering exposure, 10 hr at 410°F, as suffered by the greater part of the bainite during the isothermal transformation. About 50 pct bainite was formed in 6 hr at 410°F. On tempering at this temperature, martensite reduces its tetragonality within a few minutes to a value corresponding to 0.30 pct C.&apos; Further decomposition proceeds slowly, and after 10 hr the c/a ratio is still appreciable, i.e., 1.005. Thus, even if the bainite were to form as a tetragonal phase with a tetragonality corresponding to only 0.30 pct C, which might be assumed to coexist with e carbide, it would not be expected to become cubic in this time. It seems very likely, therefore, that bainite forms irom austenite as a body-centered-cubic phase and does not pass through a tetragonal transition. The carbon content of the cubic phase has not been determined, but it could easily be as high as 0.1 pct, within the experimental uncertainty of the lattice-parameter measurements. It has been postulated that retained austenite decomposes on tempering into the same product as martensite tempered at the same temperature. There is now considerable doubt on this point. The isothermal transformation product of both primary and retained austenite at the temperature in question here is bainite," and the present findings show that bainite and tempered martensite do not have the same matrix. Acknowledgments The authors would like to acknowledge the financial support of the Instrumentation Laboratory, Massachusetts Institute of Technology, and the United States Air Force.

Jan 1, 1957

IN THE early evening of October 15, 1954, a large specially designed truck, convoyed by a second smaller one, arrived at Silver Bell, Arizona, completing a ten-hour 110-mile journey from Phoenix. The big truck was driven through gaps left in a previously prepared concrete foundation, the load was jacked up, the large girders that constituted the bed of the truck were pulled away, and the load was then lowered into place on the foundation. A crew of two men, the two truck drivers, finished the job in a little more than an hour. When they were through, a complete and attractive three-bedroom house, prefabricated in Phoenix, was almost ready for occupancy. About all that remained to do was to connect the utilities-water, electricity, plumbing, and gas. The kitchen and bathroom equipment and appointments were superior in every respect, and there was a built-in car port for the automobile of the prospective residents. This family domicile was one of more than one hundred, each averaging about $8,000 in cost, that the American Smelting and Refining Company has provided for its employees engaged in mining and milling 7,500 tons per day of low-grade Porphyry copper ore. Aside from the fact that it is more economical-partly because of the variety of union craftsmen needed to build and equip a house-to do the work in a city 110 miles away, the significant point is the high quality of housing that is provided for what may be called in nostalgic vein the "mining camp" of 1955. Silver Bell is typical of all the Porphyries in this respect though the community is relatively small. At San Manuel

Jan 1, 1957

By H. E. Lee, D. Ingvoldstad

AT Bunker Hill the original charge storage and preparation system was installed in 1917 to accommodate lead-silver gravity mill products. Only minor tonnages of wet fines such as vanner and flotation concentrates were received. Charge flux and diluent requirements were provided by an ample supply of siderite middlings and coarse lime-rock. While oversize material was crushed through %-in., the use of roll crushers in series resulted in a more or less granular, free-running charge of adequate porosity. Under such conditions, receipts could be proportioned directly from receiving bins, and suitable blending was obtained by passing the resultant layered composite through a small Stedman disintegrator. This elementary system served well for production and smelting of an extremely lead-rich sinter, in the low column blast furnace. Here sinter physical quality is less critical, and appreciable quantities of raw flux and oxidized ore may be charged directly to the blast furnace without seriously impairing furnace capacity. Prior to 1938 the relative proportions of zinc receipts were low and extraneous flux requirements at a minimum. However, subsequent war-inflated zinc demands brought marked increase in fine concentrate and slimy zinc leach residue receipts and an abrupt introduction to smelting a more refractory zinciferous charge. The higher temperature demands of the more refractory zinciferous charge required a higher smelting column and the higher column, in turn, rendered the blast furnace less receptive to improperly prepared feed. Inadequate presinter processing facilities prevented the production of acceptable sinter, and blast furnace production declined to 50 pct of former capacity. In view of a prevailing contention among lead metallurgists as to the deleterious action of high zinc slag on blast furnace capacity, it was natural to overstress this factor and to concentrate on possible changes in furnace design. Another interpretation was that primary correction should be sought through expanded sintering facilities. This divergence of opinion, together with the extreme material shortages of the 1940&apos;s, delayed corrective

Jan 1, 1957

By Herty, C. H.

No attempt will be made here to review the previous work done by investigators on the general subject of inclusions, because it was discussed sufficiently in an early cooperative bulletin of this series (No. 36, 1928), and reference was then made to general bibliographies. The work described in this present bulletin deals directly with the study of the mechanism of deoxidation of steel with aluminum and the formation of inclusions containing alumina. Unquestion- ably, such inclusions are encountered in most steel-making practices and little has been done to determine their characteristics. Aluminum is used to ensure rapid deoxidation during the solidification stages of the steel. For this reason the possibilities of inclusion elimination are slight and alumina-containing particles will undoubtedly be present in the ingot. Besides this common practice, aluminum is often used in the ladle with other deoxidizing agents such as silicon and manganese. Ladle additions of aluminum are made to rimming steels to obtain the correct partial deoxidation desired in this type of steel. In killed steels the aluminum is added to ensure soundness, as far as blowholes are concerned, in the ingot. In either rimmed or killed steels, alumina or alumina-containing inclusions are found therein, the amount and type depending on the oxidation of the metal, the amount of aluminum added, and the addition of other deoxidizers.

Jan 1, 1957

By L. J. Ingvalson, Roy H. Miller

IN 1948, as part of a program to expand the copper tube mill facilities of the American Brass Co. plant at Kenosha, Wisconsin, plans were formulated to convert the 100 ton capacity anode casting furnace at the Great Falls, Montana plant of the Anaconda Co. to the production of 3 in. phosphor -ized billets. The furnace was rebuilt completely and construction was started on an addition to the building. Members of the Great Falls staff visited various billet casting plants to draw upon the experience of other producers of this type of casting. Many features of other plants were incorporated into the Great Falls plant but, in addition, many new designs were made and perfected to make the plant the most advanced of its type. Construction was begun in 1949, with the intention of having the plant in production in the early part of 1951. In January 1951, as the plant was being rushed to completion, the government placed restrictions on the production of copper tubing. As a result, work was halted and the plant lay idle for two years. Interest was reactivated in May 1953 with the lifting of restrictions on copper. Plans were laid to go into production in July and the first charge was taken out July 1, 1953. Basically the plant is designed to produce from cathode copper a 3 in. diam billet, 50 in. long. weighing 110 lb, and containing 0.013 to 0.036 pct P, at a rate of 150,000 Ib per operating day. These billets are to be pierced and drawn into tubing. Furnace The furnace is a 100 ton capacity reverberatory type, gas fired furnace; 21 ft long and 9 ft wide. Gas is introduced to the furnace through two 38 hole Mettler gas burners. These burners are of chrome nickel alloy with four jets per hole. The furnace is charged with cathodes from the Electrolytic Copper Refinery plus return scrap from the casting operation by means of a Wellman Seaver Morgan Co. 7,000 lb capacity charging machine. The charge crane has a 20 ft boom and fork peel provided with an air ram to push material off the peel. The machine travels on overhead tracks and can be moved in any direction. The boom can be raised and lowered and swung through an arc of 180". With well stacked units of 6,000 lb, an experienced operator can put the first charge into the furnace in 40 min. After charging, the steel framed silica brick charge door is put in place and sealed with clay. After melting and skimming off the slag, the copper is blown until an oxygen content of 0.40 pct is reached. The metal is then heated to 2180°F, covered with coke, and poled. Poling is continued until a 3 in. diam test billet, 8 in. long, shows a flat set. The oxygen content is usually 0.030 pct at this time. At the end of poling, a temperature of 2160" to 2180°F is desired. In the side of the furnace opposite the charging door is the taphole slot, extending 36 in. upward from the bottom of the furnace. It is 4½ in. wide at the outside face and widens to 9 in. at the inside face of the furnace. It is filled with a wet mixture of sand, fireclay, and crushed coal. Flow of metal

Jan 1, 1957

By E. J. Ripling

A NY mechanism proposed to explain hydrogen embrittlement in titanium and its alloys must, of course, be consistent with the experimental data that characterize this embrittlement. Unfortunately, however, the mechanical behavior of hydrogen-bearing titanium, at least a-ß titanium, has not been unequivocally defined. Lenning, Craighead, and Jaffee have clearly shown that hydrogen cmbrittles a-titanium by elevating its transition temperature, probably as the result of the formation of titanium hydrides. Therefore, in these alloys, hydrogen acts like at least one other interstitial contaminant, namely, nitrogen.&apos; On the other hand, ß-titanium has been shown by these same investigators to tolerate very large amounts of hydrogen without suffering severe mechanical damage.2 Mixing these two phases, however, to form the most important class of commercial alloys, the a-ß alloys, again results in severe hydrogen embrittlement, although the mechanism by which the embrittlement is produced is not of the same type as that which causes brittleness in a alloys. Ductility damage due to hydrogen increases as the strain rate is reduced in a-ß alloys, while embrittlement in a alloys increases as the strain rate is increased, since the latter is a transition temperature behavior. Steel, like the a-ß alloys, becomes more hydrogen sensitive at slow strain rates, suggesting that the mechanism producing the embrittlement in these two metals is similar. Brown and Baldwin&apos; described the hydrogen-produced ductility depression in steel as a function of testing temperature and strain rate by defining the slope of the two surfaces that produced the depression in a three dimensional chart, Fig. 1. One of these surfaces was given by the equations (de/de)4 > 0 (de/dT) < 0 [1] while the other was defined by the pair of equations Surfaces of the type given by Eq. 1 are suggested in two ways. One is an embrittlement mechanism wherein the diffusion rate of hydrogen is competitive with the rate at which the material is being deformed, as suggested by the planar pressure theory of Zapffe and his co-workers.&apos; The other is the diffusion controlled extension of Orowan&apos;s theory on delayed fracture in glass by Petch and Stables.&apos;&apos; Surfaces of the type given by Eq. 2 are also compatible with a mechanism of pressure build up in voids, according to de Kazinczy,&apos; since the solubility of hydrogen in the metal increases with testing temperature so that as the temperature is raised, the pressure in the voids is reduced. Kotfila and Erbin recently presented some data on the dependence of ductility on testing temperature and strain rate for the a-ß 3 pet Mn complex alloy at four different hydrogen levels.H Although data were presented for only three testing temperatures at three different strain rates, their results indicated that surfaces of the types defined in Eqs. 1 and 2 are produced in the alloy when the hydrogen level is sufficiently high—200 and 300 ppm—Fig. 2. Jaffee and his co-workers presented data on a number of different a-ß alloys which indicated the existence of surfaces of the type described by Eq. 2, but the ductility recovery at low temperatures as given by Eq. 1 was not found." In an attempt to aid in crystallizing this description of the ductility dependence of hydrogen-bearing a-ß alloys, tests were conducted by the author on a-ß titanium 140A with three different hydrogen contents. The tensile properties of two as-received rods and one vacuum annealed rod* were obtained over a range of testing temperatures and strain rates as shown in Figs. 3 and 4. Hydrogen analyses were made by the Battelle Memorial Institute on four pieces of the rod whose properties are shown as solid circles in Fig. 4. The hydrogen content of these pieces, taken at widely spaced intervals within the rod, were 280, 270, 289, and 270 ppm, indicating that the hydrogen content within a single as-received rod was quite uniform. One of the broken test pieces whose properties are shown in Fig. 3 as solid circles was also analyzed, and found to have a hydrogen content of 310 ppm. The analyses obtained on two of the vacuum annealed specimens were 92 and 170 ppm.

Jan 1, 1957

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication&apos; an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,&apos; only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement&apos; was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By G. Reinberg, C. D. Clarke

MOST underground mining operations are dependent on pumping installations to keep the mine unwatered. The reliability of such installations is obviously of paramount importance. The volume of water to be handled is often considerable, and the total head is relatively high. In these cases, both capital cost and operating expense of the pumping installations will become significant factors in overall mining costs. To insure reliability and to keep efficiencies, and hence operating cosl;s, within acceptable limits it goes without saying that mechanical maintenance of a mine pumping installation must receive scrupulous attention at all times. Large mine pumping installations today almost invariably use multistage centrifugal pumps, since positive-displacement units would not be economically competitive except under very unusual conditions of small volume combined with extremely high heads. Centrifugal pump maintenance, under ideal circumstances, would be confined to parts subject to normal running water, i.e., bearing surfaces, stuffing box packing, and shaft sleeves. Under adverse conditions, however, metal may be lost from the wetted surfaces of a pump by erosive or corrosive action of the pumped fluid, and maintenance costs can easily attain enormous proportions. The following definitions are those most generally used for the phenomena encountered. Erosion is a general term meaning mechanical removal of material from a surface. As applied to pumps, it may be the result of simple abrasion, such as that produced by suspended solid matter in the liquid being pumped. In common with other hy-

Jan 1, 1957