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By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By Ming-Kao Yen

A considerable amount of work has been reported in the literature in regard to the texture and earing behavior of copper strip. The rolling texture of copper has been confirmed as (110) [112] and (112) [111], which yields ears of a drawn cup at the position 45" from the rolling direction.1-3 The recrystallization texture has been established as the cubic or (100) [001] texture, where the earing positions are at 0" and 90" to the rolling direction.4-8 It has also been reported that in the development of cubically aligned grains of copper strips, the percentage of this cubic texture increased with an increase of final reduction and final annealing temperature.8,9 A comprehensive study on H.C. copper (British commercial copper of high-conductivity quality = Cu 99.95 pct, O2 0.03 pct, Ag 0.003 pct, Fe 0.005 pct and Pb < 0.001 pct) was made by Cook and Richards.6 They concluded that the recrystallization textures could be described as one or more of the following textures: (1) a single texture (100) 10011, (2) a twin texture (110) [112] and (3) a random orientation, depending upon the previous history of the specimen concerned. The effect of various alloying additions in copper was reported by Dahl and Pawlek.10 They found that certain alloying additions, such as 5 pct Zn, 1 pct Sn, 4 pct Al, 0.5 pct Be, 0.5 pct Cd, or 0.05 pct P suppressed the formation of cubic texture. Brick, Martin and Angierll reported that the cold rolled textures due to various additions fitted a rather simple pattern. However, the recrystallization textures were subject to very considerable variations. In the discussion of this paper, Baldwin stated that deoxidized copper containing 0.02 pct P gave a complicated recrystallization texture at lower temperature. When this copper was annealed at high temperature, a single texture appeared which was described as (110) [ill] but. according to a pri- vate communication from Baldwin, this orientation reported was in error and should have been reported as (110)[112]. He also reported that the earing positions of drawn cups were at 60" to the rolling direction.12 Recently, Howald, in his discussion on the paper by Hibbard and Yen,13 reported that the rolling texture of phosphorus deoxidized copper, containing from 0.006 to 0.020 pct phosphorus, was of the pure copper type. When these coppers were annealed at lower temperatures, they exhibited a random orientation, and when they were annealed at higher temperatures they had a mixed (111)[110] and (100)[001] texture, depending on the severity of the final reduction and annealing temperature. However, the specific influence of phosphorus and other impurities on the recrystallization textures and the deep drawing properties of copper strip has not been thoroughly reported. Therefore, an attempt has been made in the present work to determine the rolling and recrystallization textures and also the earing behavior of five types of commercial copper and thereby to evaluate the effect of phosphorus and some other significant impurities on the development of texture for cold reductions of about 87 to 89 pct. Materials Used The five types of copper employed in the present investigation were two phosphorus deoxidized coppers of different phosphorus content (0.007 and 0.013 pct P), an oxygen-free copper (OFHC), an electrolytic tough-pitch copper, and a fire-refined tough-pitch copper. These materials were subjected to a thorough spectroscopic and chemical analysis. The designations and the chemical compositions were as shown in Table 1. The coppers, FA1, FA2 and FA3. were hot-forged from 3-in. billets into a ½ X 6-in. plate and cold rolled to the ready-to-finish gauge indicated below. FA4 and FA5 were hot rolled and scalped to ready-to-finish gauge. The grain size of all the materials in the ready-to-finish condition was about 0.030 to 0.045 mm. Table 2 shows the last stage of the production schedule for each copper strip used. Experimental Procedure ANNEALING, GRAIN SIZE AND HARDNESS DETERMINATIONS Specimens of each type of copper were finally annealed in air for periods of one hour at temperatures ranging from 300 to 1600°F and were subsequently cooled in air. The average grain diameter of the annealed specimen was estimated by comparing with a standard grain size chart. Hardness was determined on the Rockwell 15 T scale. CUPPING TESTS Cups were made in a blanking and drawing set, in which blanks of 2-in. diam were drawn to a cup of 1.25-in. diam with an average depth of about 0.75 in. The clearance between the punch and die was about 0.032 in. The ears of the cup were measured with a special fixture which read the height of ears to one-thousandth of an inch on every ten-degree interval along the circumference of the cup. POLE FIGURES The usual transmission diffraction method with unfiltered copper radiation was employed to determine the pole-figures of the specimens cold-rolled or annealed at 900°F. All the pole-figures were derived from the positions of intensity maxima on 111 diffraction rings of the X ray photo-grams taken at 10 rotation of a

Jan 1, 1950

By W. Vickers

Single-point rotating cantilever fatigue tests have been carried out at 550" to 650°C on beryllium produced by a variety of fabrication routes. All the specimens gave similar plots of stress against number of cycles to failure but failure occurred at a lower stress range in the hot-pressed material than in the extruded material. A discontinuity or "kink" appears to exist in the curves and this is considered. A true endurance limit was not evident up to 10 cycles. When Brush hot-pressed warm-extruded beryllium was tested at 600oC a relationship where Nf = number of cycles to failure, ?ep = plastic strain range, and c = constant, was shown to be applicable for values of ?ep > 6.3 x 10-4. Further for this moterial and temperature and for frequencies between 150 and 4500 cycles per min, the variation of number of cycles to failure with frequency obeyed the expression N = Af0.44 where N =number of cycles to failure, f = frequency, and A = constant. Examination of the fracture surfaces indicated that they were generally intergranular and in all cases the higher the stress the more irregular was the fracture. Microexamination has shown that grain boundary cavities and fine intergranular cracks were associated with the fractures. REVERSING or cyclic stresses set up in fuel elements can lead to failure by fatigue. Fatigue stresses may be developed by instability of the fuel element in the coolant flow leading to rattling against the channel wall or fin vibration. Thermal cycling also sets up reversing stresses due to differential expansion of fuel and can. Fatigue resistance is of some importance therefore in the evaluation of canning materials. At the time the work described in this paper was initiated, beryllium was being considered for the can and endcaps of an advanced gas-cooled reactor fuel element. With this in mind, beryllium obtained from different manufacturing routes was tested on single-point rotating cantilever fatigue machines at temperatures the same as those envisaged in the reactor to obtain appropriate fatigue data. The results obtained indicated a discontinuity in the S-N curves coinciding with the yield stress in the specimens. Although in some cases the data is insufficient to warrant a detailed quantitative analysis, a qualitative analysis of this effect was thought to be justified. 1) EXPERIMENTAL DETAILS The materials used are given in Table I together with the production route and available analyses. The specimen shape is shown in Fig. 1. The fatigue specimens were machined slightly oversize, after which they were given a stress-relieving anneal of 1 hr at &apos;750° C in vacuum. This was followed by an etch in sulfuric-phosphoric-chromic acid mixture down to the finished dimensions given in Fig. 1. Etching served to remove the interference colored oxide film formed on the surface during annealing and very small recrystallized surface grains too. The specimen was mounted in the grips of a cantilever machine and rotated inside a furnace controlled at the testing temperature. The specimen was loaded in increments as the speed was increased until the required load was applied at 5000 cycles per min. A revolution counter was used to record the total number of cycles.

Jan 1, 1964

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

By R. M. N. Pelloux

This study of aluminum-copper alloys had two aims: 1) To determine the effect of the amount and distribution of a second phase, CuAl2, on the creep-rupture strength, ductility, and fracture characteristics of the alloys. The work of Gemmell and grant&apos; on single-phase aluminum-copper alloys provided a basis for the present study. 2) To attempt to provide a relation between the microstructure and strength of two-phase alloys deformed at comparatively high temperatures (greater than 0.45 T,). The creep behavior of the two-phase magnesium alloys Mg;Ce and Mg-A1, has been treated by Roberts. 9 In work reported by Sully and Hardy4 and by Underwood, Marsh, and Manning~ on A1-Cu two-phase alloys, and also in a portion of the work of Gemmell and grant,&apos; aging took place during the creep tests. &apos;In the present work, overaged aluminum-copper alloys were subjected to creep deformation at two temperatures, 500 and 700OF. The overaging treatments to produce the precipitate dispersions were performed prior to the test, at temperatures which were the same as the ultimate respective test temperatures. Hence, the present study is concerned with the creep behavior of stable (in contrast to "underaged") two-phase A1-Cu alloys, i.e., alloys in which no depletion of the solid-solution matrix occurred during: creep. MATERIALS AND PROCEDURE A 2 and a 3 pct Cu alloy, supplied by Alcoa, were studied; Table I shows the compositions. The grain size of the specimens, 0.9 to 1.0 mm, was achieved by annealing the machined test bars for 2 hr at 1000°F, followed by furnace-cooling to 900°F, and homogenizing for 4 hr. Both compositions are in the single-phase condition at 900°F. Two types of overaged dispersions, termed "over-aged I" and "overaged 11" were prepared after the grain size and the homogenization anneals. The overaged I alloys were prepared by quenching to room temperature after homogenization, aging at either 500&apos; or 700°F for 72 hr, and air-cooling to room temperature. The overaged I1 alloys were prepared by furnace-cooling after homogenization, to either 500&apos; or 700°F, and holding at the necessary temperature for 72 hr. The times for furnace-cooling from 900°F to 700° and 500°F were, respectively, about 2 and 3.5 hr. The structures of the A1-2 pct Cu alloys are shown in Fig. 1 (overaged I) and in Fig. 2 (overaged 11). A comparison of Figs. 1 and 2 shows that in the overaged I alloys the precipitate particles along the grain boundaries are much more closely spaced and the grain boundaries are straighter than they are in the overaged I1 alloys. Further, the particle size and spacing in the grains are smaller than in the overaged I1 alloys. Microstructures of the A1-3 pct Cu alloys have not been shown; the structures of these alloys differed from those of the A1-2 pct Cu alloys only in that the distribution density of the particles was greater. The creep specimens had a gage section 1 in. long with a diameter of 0.155 to 0.195 in. Before testing, specimens were electropolished in a solution of 100 cc glacial acetic acid, and 30 cc of 60 pct perchloric acid, at 40&apos; to 50°F, at 24 v. The specimens were kept refrigerated prior to testing to avoid precipitation at room temperature. Constant stress creep tests were conducted; the load was applied 75 min after heating of the specimens to test temperature had begun. EXPERIMENTAL RESULTS Creep-Rupture—Fig. 3 shows the log stress-log rupture life plotfor the overaged alloys studied, and also for the underaged A1-2 pct Cu alloy.&apos; At 700°F, the stress-rupture life relationship is nearly independent of both the amount of precipitate (i.e., composition) and of the type of overaging treatment (i.e., precipitate dispersion). At 500°F it is apparent that the increase in rupture life that was ex-

Jan 1, 1960

By C. Dalton, H. L. McGill

The purpose of this study was to develop a method for predicting the time delay created by metering a fluid through an annular restriction with translational motion of the boundaries. This time delay is utilized to control the opening of valves in various down-hole oilfield tools and forms the basis for the "hydraulic jar". The hydraulic jar is used to give upward impact forces to tubing or other tools that become lodged down-hole. The design of these jars has primarily been by trial and error; varying the clearances, fluid viscosities and dimensions of the jar until a satisfactory time delay was achieved. Obviously, a better understanding of the fluid flow characteristics is required to produce designs that are satisfactory and to eliminate the trial-and-error approach. Previous studies of flow in annular spaces were based on constant length of the annular restriction. Any motion of the boundaries of the annular space was confined to a rotational motion, like that encountered in journal bearing design. Consideration of the effect of translational motion of one boundary with respect to the other was necessary in applying this previous work to a time delay device. A prediction method was developed that takes into account this relative translational motion. Equations were developed to predict the relative velocity, the flow rate, and the time delay in a concentric annular space. The effect of eccentricity also was included. Experimental data were obtained and closely correlated with the prediction method. This correlation is presented graphically in terms of predicted and actual relative velocities for various annular clearances and pressure drops. This extension provides design equations which predict the performance of the hydraulic jar, thereby eliminating trial-and-error solutions and reducing the development time required for satisfactory designs. INTRODUCTION The design of down-hole oilfield tools which use hydraulic delay systems based on flow through annular orifices with relative motion of the boundaries is usually a trial-and-error process. The annular clearances, fluid viscosities and dimensions of the mechanisms were varied until satisfactory delay times were obtained. The development of these tools has been expensive, and a better understanding of the characteristics of annular flow with relative motion of the boundaries could result in superior and less expensive designs. The purpose of this investigation was to provide a method of predicting the performance of down-hole tools which use annular flow and, in particular, the performance of a down-hole tool known as the "hydraulic jar". The hydraulic jar is used to free pipe, packers and other tools that become lodged down-hole. The jar, located in the tubing string between the surface and the object which is stuck, releases the object though the repeated application of upward impact blows. The jar is basically a slip joint that is restrained in a collapsed condition until the desired tubing tension has been developed. The slip joint is then released and accelerates rapidly until it shoulders, delivering an impact blow or jar to the object. The delay obtained by metering the fluid through the annulus formed by the jar valve and housing provides the time delay necessary to stretch and apply tension to the tubing or pipe. Fig. 1A gives a schematic diagram of the hydraulic jar and brief details of its operation. The metering of the hydraulic jar begins when the tension force being applied to the jar by the pipe creates a pressure differential across the valve that is approximately equal to the force divided by the displacement area of the valve. This pressure differential induces flow through the annular restriction formed between the valve and housing. The valve moves with respect to the housing as the

Jan 1, 1969

By N. J. Grant, H. Brunner

This paber is concerned with the determination of equations relating elongation to the amount of shear taking place both along grain boundaries and in slip planes of poly crystalline aggregates during creep. Certain discrepancies with previously used equations are pointed out. Grain boundaries were observed to become serrated during creep, but it is shown that this does not necessarily prevent further grain boundary sliding. Direct obser-vations of subgrain boundary ingration lead to the conclusion that this migration facilitates sliding along serrated grain boundaries. It is bointed out that the state of stress at triple boints is still unknown. MOST of the mechanisms of deformation contributing to elongation are shear processes, such as slip, kinking, grain boundary sliding, and twinning. For quantitative investigations of individual deformation mechanism it is necessary to know the equation which permits the calculation of speci-tnen elongation from measured amounts of shear. This calculated elongation must then be compared with the observed total elongation. The authors&apos; special interest concerned grain boundary sliding during creep. Although this subject has already been investigated quantitatively by McLean,&apos; Rachinger,&apos; and Fazan, Sherby, and Dorn, calculations indicated that none of the equations used thus far to relate shear with elongation were sufficiently well founded. A basic study of this relationship was thus made and the results of this study (which do not entirely agree with those previously used) are presented. Most of the ideas set forth apply not only to grain boundary sliding but to other mechanisms of shear as well. THE SPEAR-ELONGATION RELATIONSHIP Basic Models—The relationship between shear and elongation is trivial in the simplest case of shear, which is shown in Fig. l(a). The vector A; designates the displacement across the shear interface, and Au, and Aut are its components parallel and normal to the tensile direction, respectively. It is evident that the specimen elongation due to shear is equal to the longitudinal component of the shear vector, and it should be noted that the normal component does not contribute to the elongation of the specimen (there are, of course, two normal components in a three-dimensional model). The model shown in Fig. l(b) may be applied to mechanical twinning and to subgrain boundary tnigration. In this case the width (h) of an already existing shear band increases by the migration of an interface, but the shear angle y (angle of mis-orientation in the case of a subgrain boundary) remains constant. The geometrical relationships indicated in Fig. l(b) permit this case to be reduced to the one shown in Fig. l(a). For the resulting elongation A6 we find: where AV/V = fraction of the volume of the specimen swept by migrating interfaces , and 1 = length of specimen. Thus, assuming for example that the angle of mis-orientation is 1 deg, and that P = 45 deg, we find that the specimen elongates 0.87 pct of its length if the entire volume of the specimen is swept once by such a subgrain boundary. An example of deformation by migration of subgrain boundaries is shown in Fig. 2. The specimen shown was repolished after 9.8 pct creep strain and the test then continued for another \ pct. Since the shear vector has, in general, a component normal to the surface, subgrain boundary migration results in the formation of an inclined band delineating the region swept by the subgrain boundary. These inclined bands become clearly visible when observed with oblique illumina-

Jan 1, 1960

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.&apos; The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By Robert U. King, John W. Vanderwilt

THE Climax molybdenite deposit in Lake County 100 miles southwest of Denver is located in the central part of the mineral belt extending northeasterly across the state. Principal geographic features and geology are shown on Fig. 1. The first period of molybdenite mining, which began in 1918, ended in April 1919 because of limited demand and a price drop to about 72¢ per lb. During this time the ore came from the Leal level and surface outcrops at a higher elevation. Rate of mining was 250 tpd and several million tons of ore averaging 0.7 pct molybdenite were developed. Since April 1924, when the second period* began, Climax Molybdenum Co. has been the only operating company. Production in 1924 was 400 tpd and finding ore was a continual problem. When the White tunnel was extended, however, further ore was encountered. The orebody was thought to be tabular until 1926, when B. S. Butler recognized the relation of the developed ore on the Leal and White levels to a central area of fine-grained hydrother-mal quartz, and by 1929 diamond drilling had blocked out indicated ore reserves in excess of 100 million tons. In 1946, on the basis of information obtained from 25 miles of mine workings and a completed exploratory program involving over 200,000 ft of diamond drilling, the present authors reviewed and brought up to date the geology of the orebody. More recently Sears," employing microscopic techniques, made a study of hydrothermal alteration and mineralization, and Howell and Schassberger&apos;" restudied available geologic data. Production (1953) of molybdenite ore has been expanded to over 25,000 tpd and total production from 1918 through 1953 has been: Tungsten, tin, and pyrite are byproducts and monazite also was produced from 1949 through 1951, after which it was not saved. A maximum of 15 to 20 tons of monazite was produced. Geology of the Area Pre-Cambrian crystalline rocks constitute most of the Mosquito Range for several miles to the north, east, and south of the Climax molybdenite deposit, see Fig. 1. To the west the crystalline rocks are in fault contact with shales and sandstones of Pennsyl-vanian age. Both crystalline rocks and sediments are intruded by dikes and sills of Tertiary age. Numerous faults with small displacements are to be found in the crystalline rocks east of the Mosquito fault and in the sedimentary beds to the west. Pre-Cambrian Rocks: The pre-Cambrian rocks consist of schist and gneiss, identified with the Idaho Springs formation, and granite with minor pegmatite correlated with the Silver Plume granite of the Silver Plume area. The Idaho Springs formation is a general term applied to pre-Cambrian schist and gneiss found over a large part of the Colorado Front Range. At Climax this formation consists largely of biotite-schist and quartz-biotite gneiss with minor quantities of plagioclase and orthoclase, although in places appreciable quantities of feldspar and quartz are present in the more gneissic varieties. Locally, especially along the contact with granite, recrystal-lization of the schist has produced coarser texture and a more pronounced than average gneissic appearance. The gneiss and schist have been mapped as a single unit by Butler and Vanderwilt (1933)" and by Singewald (1951).12 Schist predominates at the higher elevations of the Mosquito Range and in the area to the north and east of Climax. The regional trend of schistosity is northeast with varying dips to the east. Silver Plume granite and associated pegmatite intrudes the Idaho Springs formation. Silver Plume granite in many places and in the Climax district in particular has an irregular form, and many large and small inclusions of schist and gneiss occur within the granite. Granite predominates at the surface in the immediate vicinity of the area of hydrothermal alteration and extends for several miles to the northeast and southeast. As more schist is present at lower levels of the mine than in the upper levels, the suggestion is that the granite is sill-like in form,

Jan 1, 1956

By C. F. Allen, G. B. Walker

The sink-float methods designated by heavy-media separation processes were pioneered by C. Erb Weunsch for the treatment of base metal ores as an improvement over jigs. The work of Weunsch was further developed by Victor Rakowsky and The American Zinc, Lead and Smelting Co. Early in the development of the processes, the inherent unsuitability of galena as the solid constituent of the medium was recognized and ferrous media amenable to magnetic recovery and control were developed. The high efficiency and low cost of magnetic recovery and cleaning of ferrous media regardless of particle size, slime contamination, or surfacial oxidation had led to the adoption of ferrous media by all of the sink-float plants operating under the heavy-media separation processes patents controlled by American Zinc, Lead and Smelting Co. Approximately 2,000,000 tons of base metal and nonmetallic minerals are treated each month by these methods. Heavy-media separation processes are a modern practical and economical adaptation of the well-known laboratory procedure for separating a mixture of two solids by immersing the mixture in a liquid having a specific gravity intermediate the specific gravities of two solids. The lighter solid floats while the heavier sinks. This method of separation has been attempted on a commercial scale, but the high loss and high cost of the organic liquids halted the development of the process. Many attempts have been made to simulate a heavy liquid by using a suspension of a finely divided solid in water. If the solid phase of the suspension is ground fine enough, the suspension can be made stable or so slow settling that a substantially uniform specific gravity can be maintained from top to bottom of the bath. However, any material separated by such methods will inevitably be contaminated by some slime which will eventually accumulate in the bath and cause a viscous medium at the expense of separating efficiency. Therefore, it is necessary to provide means for continually cleaning a portion of the medium to eliminate slime at the same rate at which it is introduced to the medium. The problem of efficiently cleaning the medium limits the minimum grain size of the solid of the suspension in the case of the Chance sand process for cleaning coal, because de-cantation is the only cleaning method available. If the sand is too fine, it will be lost along with the slime. Therefore, coarse sand must be used, and to maintain a semblance of a uniform suspension, it is necessary to use strong rising water currents. The combination results in a separation based more on hindered settling classification than on sink-float principles. As previously mentioned, galena was used as the solid constituent of the medium during the early stages of the development work. The high specific gravity of galena made it suitable for the preparation of medium for high specific gravity separations. Galena can be cleaned by either decantation or by froth flotation. As with sand, de-cantation limits the minimum particle size of the media that can be cleaned without excessive loss. Froth flotation for cleaning galena medium has been used, but the problem of floating fine galena that has been exposed to extensive oxidation is well known to be a most difficult one. Last year the largest heavy-media plant m the world, and the second plant to be installed, converted from galena medium to ferrous medium despite the fact that the ore contains galena which can be used as medium. The change to ferrous medium has been beneficial in many ways. Today all the heavy-media plants have been converted from galena to ferrous media. Unquestionably, ferrous media have the widest application of any media developed, for the following reasons: 1. Ease of recovery and cleaning by magnetic means. Particle size or surface condition not a factor. 2. Low consumption per ton of ore treated. 3. Resistance to abrasion. 4. Widest range of media densities, including higher workable densities (1.25 to 3.4) than have been found possible with nonferrous media. 5. Space required for recovery and cleaning of ferrous media is considerably less than that for nonferrous media. 6. Ferrous media require lower capital investment and operating costs for media recovery and cleaning. Advantages of Heavy-media Separation Processes Heavy-media separation processes offer the following positive advantages, amply demonstrated on a wide variety

Jan 1, 1950

By F. H. Vitovec, D. W. Hoeppner

Pusk-pull fatigue tests were conducted on copper tricrystals of 99.988 pct purity to ascertain the role of grain boundaries in the initiation and propagation of fatigue cracks. Significant differences in behavior were found for specimens which possessed different transverse-boundary misorientation. In speciwens with low boundary angles cracks initiated within the transverse boundary, while higher angles led to transcrystalline fatigue failure. It is suggested that at low angular misorientation moving dislocations may interact with dislocations of the boundary or dislocations present in adjacent pains on favorably oriented glide planes, thus initiating a fatigue crack. MANY fatigue studies have been concerned with fatigue-crack initiation within grains and the mechanism causing initiation and propagation1-3 Although the initiation of fatigue cracks in or near grain boundaries of pure metals has been observed and reported in the literature, the mechanism of this phenomenon has received little attention.4"11 EXPERIMENTAL PROGRAM Testing Procedure. To investigate the role of grain boundaries regarding initiation and propagation of fatigue cracks, copper tricrystals were tested in push-pull. Axial-stress tests were used to avoid the stress gradients introduced by stressing of some other nature. Copper was selected as the most suitable test material since extensive work has been done on the formation of fatigue-induced slip in copper. Tricrystal specimens were used to provide a grain boundary geometry with one boundary transverse to the principal stress axis and one or more boundaries nearly coincident with the direction of maximum resolved shear stress. The boundary energy and the slip characteristics in the vicinity of the transverse boundary depend on the relative orientations of grains across the boundary. Testing was done at room temperature, at a frequency of 700 cpm, in an atmosphere of either air or argon. It is known that the incidence of grain boundary cracking increases with increasing temperature and decreasing frequency.4 The fatigue machine applied a uniaxial tension-compression load to the specimen by a flat spring which was actuated by an adjustable eccentric. Use was made of an adjustable head and a load cell which had strain gages mounted at 120-deg intervals around its periphery, thus providing a means for eliminating any detectable superimposed bending moment. A clip gage was mounted between the gripping heads to record the cyclic strain amplitude applied to the specimen. Each specimen&apos;s hysteresis characteristics were recorded by supplying the load and strain signals to an oscilloscope. Microstructural changes were observed and recorded with an optical microscope which was mounted on the fatigue machine. Immediately prior to insertion in the machine, each specimen was chemically polished. Extreme care was exercised while inserting the specimen in the test machine to avoid either bending the specimen or introducing a mean load. Each specimen was stressed in the tensile direction first and subsequently the load was reversed. Specimen Preparation. Tricrystal fatigue specimens of 99.988 pct Cu were grown from the melt using a modified Bridgman technique. Ingots about 1 in. high were grown to the configuration shown in Fig. 1. Upon sectioning the resultant ingot, several specimens were provided with an identical shape and grain boundary orientation. Except for plane sectioning and final polishing, this method eliminated machining the specimens. The apparatus used for growing the tricrystals is shown in Fig. 2. A spectrographically pure graphite mold, Fig. 3, was inserted in a vycor tube which was mounted on a vertical zone-refining table. Prior to insertion in the tube the mold was assembled as follows. The insert and graphite rods were fixed in position in the mold. The copper was then placed in the mold and the entire mold assembly was positioned in the vycor tube, Fig. 2. At this point the tube was sealed, evacuated, purged with helium gas, and finally placed under a slightly positive helium pressure. The heating coil was then adjusted to melt the copper charge, after which it was raised at a speed of 4 in. per hr. It is also possible to use

Jan 1, 1964

By B. Herrlander, A. Hultgren

The original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between A1 and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880&apos; was free from veining. Bannister and Jones&apos; considered veining in ferrite to be a manifestation of microscopical and sub-microscopica~ inclusions. NorthCOtt,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berg1und. TrittOn (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling. Slight distortion would not allow projecting parts of a growing crystal to join up with atomic symmetry. Hanemann and co-workers showed that veining in ferrite consisted of ridges

Jan 1, 1948

By W. R. Kanne, P. R. Strutt, R. A. Dodd

A study has been made of the creep behavior of ß-NiAl of stoichiometric composition in the temperature range 475" to 775°C. Single crystal tensile specimens were deformed under a constant applied load. From slip line studies and tensile axis rotations it was concluded that the crystals deformed by pencil-glide on (100) and (110) planes with a (100) slip direction. Electron microscope thin-film studies showed evidence for profuse cross-slip, and the dislocation Burgers vector was determined to be (100). There was no tendency for the dislocations to lie in definite slip planes, although a strong alignment of segments of edge dislocations was frequently seen. The activation energy for creep in the temperature range 475" and 775°C was judged to be much lower than that for creep at temperatures above 775°C. It is possible that the rate-controlling process is the thermally activated cross-slip of screw dislocations. In recent years considerable interest has developed in the possible use of high-melting-point intermediate phases for high-temperature applications necessitating good creep resistance. Ordered alloys such as Ni3A1, modified by alloying additions, have received particular attention, culminating in the recent development by Pratt and Whitney of single crystal turbine blades.&apos; The intermediate phase NiAl has considerable theoretical interest from a creep standpoint because not only is it ordered up to the melting point (-1650°C at stoichiometry) but it contains a high concentration of structural vacancies on the aluminum-rich side of stoichiometry. These vacancies are known to exert a strengthening effect under some conditions,&apos; but in addition they might be expected to affect high-temperature creep rates through dislocation climb. The present paper deals with the slip line and dislocation structures developed during creep of stoichiometric NiAl between 475" and 775C, and with possible attendant creep mechanisms. MATERIALS AND TEST TECHNIQUES NiAl ingots of stoichiometric composition were prepared by induction melting 99.996 pct A1 and 99.98 pct Ni (kindly provided by the Kaiser Aluminum Co. and the International Nickel Co., respectively) in 100 cc pure alumina crucibles in a helium atmosphere. No chemical melting flux was used in order to avoid con- tamination of the alloy. Each ingot was slowly direc-tionally solidified to avoid porosity and to produce very large grains up to 2 in. in length. In this way, ingots were obtained which were suitable for sectioning into single crystal creep specimens. Chemical analysis indicated that all alloys were within the range 49.6 0.3 at. pct Ni. For the present investigation, identical rectangular single crystal blanks were cut vertically from one particularly large crystal in an ingot using a series of three diamond cut-off wheels with appropriate spacers. Thus, all sliced crystals had the same orientation with the tensile axis parallel to the long side of the rectangle; the initial orientation of the tensile axis is shown as S, in Fig. 1. The blanks were homogenized at 1250 to 1300°C for 48 hr and subsequently cooled slowly to room temperature. A gage length of rectangular cross section and about 0.75 in. in length was prepared on each specimen using an electrolytic lathe and a dilute nitric/phosphoric acid electrolyte. The gage length cross section was 0.250 0.0005 in. by 0.040 ± 0.0005 in. Holes to accommodate tensile grips were electrolytically machined using a rotating acid jet. After creep testing, this same technique was used to cut discs for transmission electron microscopy. Thus, all shaping was done electrolytically, the only exception being that (122) sections were spark-machined from some speci-

Jan 1, 1970

By Glenn C. Waterman

THE diamond drill is a very important tool in exploration and development testing and its use is increasing. In almost all cases results of diamond drilling are analyzed on the basis of grade and tons. A proper evaluation of core and sludge assays is important if drilling results are to be acceptable as a basis for geologic and engineering appraisal. The relatively wide variation in assay averages as calculated by various well-known combining methods indicates that the engineering choice of a method may affect the outcome of the drilling in terms of ore and waste. The problem of combining assay results from core and sludge samples has been discussed many times in conference and in the literature.&apos;-&apos; Most writers agree that the field of disagreement in methods is large and that the engineer on the job must consider features unique to his drilling, pick one of several combining methods, and depart from the rules when abnormal results come in. All the discussion to date can be summed up by the admission that as yet there is no fairly simple, generally acceptable combining method that is practicable over a wide range of drilling conditions, ground conditions, and ore occurrence. The combining problem is important in evaluating drilling results at Chuquicamata. Recently a reappraisal has been made of recovery variables and their effect on assays, with the result that a new combining method is offered which fits average drilling conditions and is mathematically reasonable. It is simple in application, fundamentally correct, and an improvement over most combining methods. At Chuquicamata diamond drillholes are used to outline the grade and position of blocks of normal and marginal grade oxide, mixed, and sulphide ore. Most holes penetrate all classes of material (and waste), and it is important for mining programs as well as ore reserves to know almost precisely the soluble and insoluble copper content of mineralized ground. At present three classes of ore are mined and treated differently. For an orderly sequence of mining operations which can provide regular daily tonnages of all three ore types and keep grade at certain levels with minimum variation, ore type and its grade must be predicted. Diamond drilling plus geologic mapping and bench sampling are tools for prediction. And drilling data are largely used to calculate grade of material more than a few meters away from bench faces. The orebody at Chuquicamata" is criss-crossed by millions of barren or mineralized weak to fairly strong slips and fault fissures. Mineralization is diverse and encompasses many quartz and oxide or sulphide-bearing copper veins, as well as seams and disseminated grains. Copper occurs in oxide or sulphide minerals or mixtures of these two mineral types. Rock conditions vary from intensely seri-citized (soft and porous) through clay-altered ground to almost fresh granodiorite. The result is an orebody which offers many obstacles to good and consistent core recovery in diamond drilling. Recovery varies considerably in the several alteration zones, the various types of oxide and sulphide ores, and the position and inclination of the drillhole within the complex fracture pattern. As core recovery drops sludge samples must be used with core samples to calculate grade. Many years of drilling at Chuquicamata indicate that in good grade oxide zones and in the sulphide areas core recovery is good and the ground uniformly mineralized. Moderate loss of core, therefore, does not markedly affect grade calculations based on core assays. An early core-sludge combining method used core assays at face value as indicating grade down to 50 pct core recovery, but below this recovery percentage sludge samples were used and weighted according to the standard Longyear chart. This method apparently did not introduce serious errors, but it abruptly used sludge assays with high weighting factors representing 100 pct return irrespective of actual percentage of sludge recovered. Recent drilling activities have been directed toward outlining the marginal ore areas. The non-uniform mineralization and generally poorer core recovery in such ground indicated that a more exact core-sludge combining method was required to equate wide differences between core and sludge assays and recovery. In fringe ore areas at Chuquicamata core recovery averages about 50 pct, from a minimum of 10 to 15 pct to a maximum of 100 pct. Sludge recovery is likewise variable and averages perhaps 80 pct even though holes are cemented as water return falls off. In a homogeneously mineralized area cut by many slips and faults, with hard and soft ribs, loss of core is loss of ground which has a grade similar to that of core recovered, and core assays approximate true grade. In this case sludge samples need not be used. However, it would be unusual to know beforehand that an area is uniformly mineralized, and in fact this condition is probably uncommon. Generally the distribution of valuable minerals in the ground does not exactly compare with their recoverability in core. Thus, in the usual case, loss of core decreases the

Jan 1, 1956

By J. B. Clark, A. J. McEvily, R. L. Snyder

The nonuniform distribution of precipitate particles has been recognized as a leading factor contributing to the relatively low fatigue resistance of aluminum alloys. The structure of many of these alloys is characterized by narrow precipitate-free zones adjacent to the grain boundaries. Alloys with such zones exhibit a tendency for brittle inter crystalline fracture. The interrelation between this type of structure and mechanical properties was investigated in an Al-10 wt pct Mg alloy. It was found that deformation during fatigue occurs preferentially along these zones and cracks initiate there. In Al-10wt pct Mg, the zones were found to be supersaturated even after extensive general precipitation and are due to the absence of proper precipitate nuclei in the region near the grain boundaries. Cold working the alloy prior to aging improves the mechanical properties by inducing precipitation within the zones and also by jogging of grain boundaries. The mode of fracture is changed from brittle inter crystalline to more ductile trans granular fracture. THE process of fatigue is highly structure sensitive, with the strength of the whole often dependent upon some localized discontinuity, either geometrical or metallurgical in nature. Much has been learned about the role of geometrical discontinuities, e.g., notches, in fatigue, but with the exception of the effects of inclusions or the shapes of carbides, relatively little is known about the specific effects of discontinuities in metallurgical structure such as nonuniform precipitation. In most age-hardening aluminum alloys, metallo-graphic studies have shown that the extent of precipitation adjacent to grain boundaries is much less than that which occurs in the interior of the grains. The width of these almost precipitate-free regions, which are sometimes called denuded zones, and the extent of solute depletion within them, are dependent upon the particular alloy and its aging treatment. It has been observed1 that these zones are relatively soft with the result that plastic deformation takes place preferentially within them. It has also been shown 2-4 that there exists a tendency for intercrys- talline cracking in fatigue when such zones are present. It is of interest to note that Broom et al.2,3 were able to reduce the incidence of this type of failure in an A1-4 wt pct Cu alloy by stretching the material 10 pct prior to aging. In the present study, the effects of precipitate-free regions on the fatigue properties of an A1-10 wt pct Mg alloy were studied in detail, and the effects of deformation prior to aging on the nature of the precipitation process as well as on fatigue properties were also investigated. MATERIAL AND PROCESSING An A1-10 wt pct Mg alloy was selected for this study, because it was known that well-defined precipitate-free regions along the grain boundaries are readily obtained in this alloy after aging at 200oC.5 The starting materials were 99.998 pct A1 and singly sublimed magnesium of about 99.9 pct purity. The aluminum was induction melted in a graphite crucible, and then the magnesium addition was immersed until dissolved. Chlorine gas was then bubbled through the molten alloy for 4 min to degas the melt, after which the melt was cast at a pouring temperature of 730" to 760°C into a cold, graphite-coated, tapered steel mold. Since A1-Mg alloys are difficult to homogenize,5 special care was taken to obtain a uniform composition. Two-in. cubes were cut from the ingot and heated at 446°C for 30 min. These cubes were then hot forged approximately 35 pct in each of the three cube directions and homogenized for 16 hr at 446°C. Sheet specimens were then obtained by pressing 40 pct and rolling 35 pct per pass with reheating between reduction steps to a final thickness of approximately 0.10 in. The sheet was then solution treated for 16 hr at 446°C and water quenched. The age hardening behavior of this material at 200°C was then determined, and the results are shown in Fig. 1. The age hardening of this alloy when subjected to cold work prior to aging is also shown in this figure. Preliminary work indicated that extensive deformation after quenching was required to affect drastically the precipitate-free regions in this alloy, and a rolling reduction of 50 pct was chosen. For purposes of comparison the following three conditions were studied: a) Solution treated, quenched, and aged 20 hr at 200°C

Jan 1, 1963

By J. J. Arps

n approach to the study of the electrical properlies of drilling muds, their cakes and their filtrates was made by treating the drilling fluid as a porous medium. Lluring this study it was found that the weight pararneter was omitted from previous investigations on electrical properties. Patnode in 1949 made a similar approach to ,his investigation. His work showed that there was a variation of resistivity relationships with per cent Puid present in a given suspension. This present study ex-tends Patnode&apos;s investigation to one in terms of the solids fraction of the drilling fluids. Previous investigations were made on low weight muds where the effect of the rolids fraction was obscured. The following equationr were fitted to data taken from 94 field muds and 47 laboratory muds (see Tables I and 2). The parameter, C, is a complex function of the solidr content, or mud weight, of a drilling fluid. It was also found that for all drilling muds examined. A nomograph is presented combining Eqs. I and 2. INTRODUCTION It is generally recognized that the materials present in drilling muds affect the relationship between mud filtrate and mud resistivities. However, most electric log interpretations proceed with the assumption that the mud resistivity and temperature are the only important parameters needed to obtain a filtrate resistivity or a mud cake resistivity. Lamont1 suggests that only average relationships exist between mud cake, mud filtrate and mud resistivities. He indicates that there is limited accuracy when these intercorrelated factors are used since no other measure-able variable is apparent. A previous paper by Patnode indicates that drilling fluids may be considered to be a system of fluids in solid particles which may be correlated electrically in a manner similar to rock solids. 1 he equation for the resistivity factor. F = (per cent fluid) is satisfied for a given clay type in water, but the value of m varies as different materials are used in the water. The resistivity factor is not constant for a given amount of clay. As is suspected it varies as the solids fraction conducts electrical current. Since both weighting material and clay solids are present in commonly used drilling fluids, it is expected that both materials contribute to the variation of the m factor in Eq. 3. An extension of Patnode&apos;s work is presented in this paper to show some of the interrelations which exist between the resistivities of mud cake, mud filtrate and mud. Use of these data enable a more accurate calculation of mud filtrate and mud cake resistivities if only the mud resistivity and weight are measured. EXPERIMENTAL The measurements of mud weight, fluid and solids resistivity, alkalinity, and chloride content of mud samples were made in this research. Mud samples representing drilling fluids from 94 Louisiana and Texas wells (Table 1) and 47 laboratory-constructed systems (Table 2) were used in the experimentation. The measurements of the mud properties were made both in the field and in the laboratory. The tests on the properties of weight, alkalinity and chloride ion were standard tests as described by API specifications. The resistivity measuring devices were constructed in the laboratory for this study. For details on the resistivity equipment see Fig. 1. The fluid cell

By R. S. Wagner, W. C. Ellis

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication&apos; described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .&apos;whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.&apos;" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By J. Sibakin, R. D. Hindson

In order to devise a practicable soaking pit schedule for use at The Steel Co. of Canada Ltd.&apos;s Hamilton Works, soaking pit heating temperatures, sooking times, pit capacity, and safe maximum mill drafts were correlated with fluctuations in the current or load of the bloom mill driving motor. Other variables such as total delays in the pit, rolling schedules, mill delays, and track times were also investigated. IN order to show an easily applied and accurate means of establishing soaking pit heating temperatures, soaking times, pit capacity, and safe maximum mill drafts, these various factors are correlated herein with fluctuations in the current or load of the bloom mill driving motor. Rolling practices have a considerable influence on the production capacity of a blooming mill. The maximum values of the torque, in particular, are of importance, since even instantaneous current peaks lead to the tripping of the motor by the overload relay and result in loss of mill time. The establishment of safe maximum drafts and accelerations for ingots of different sizes and of a soaking pit practice which would ensure a consistent and satisfactory plasticity of the metal is of considerable importance for increasing the efficiency of both the blooming mill and the soaking pits. The Bloom Mill Dept. of the Hamilton Works, The Steel Co. of Canada Ltd., is equipped with one 44 in. mill driven by a 7000 hp motor with the setting of the overload relay at 22.0 ka. The speed of rotation of the motor is regulated after the Ward-Leonard system. There are three basic speeds of 9.5, 28, and 47 rpm and a further possibility of increasing the speed by weakening the field. This last possibility is hardly ever used during practical operations. The rolling program of the blooming mill is varied, both in the size of the ingots to be handled and in the steel grades. The total tonnage handled by the mill is about 2,000,000 ingot tons per year. At the time of the investigation, the Bloom Mill Dept. was equipped with 22 soaking pits (6 regenerative, 14 bottom-fired, and 2 one-way top-fired pits) with a total bottom area of 2770 sq ft. The pits are fired with a blast furnace-coke oven gas mixture having a calorific value of 155 Btu per cu ft. The foregoing figures show that the production program was such as to impose the necessity of a most efficient usage of the available equipment. For this purpose, the operations of the 44 in. mill and of the soaking pits were investigated, and the results of the investigation were used as a basis for a revised soaking pit schedule and drafting practice. The plasticity of an ingot of a certain chemical composition when being rolled is determined mainly by the following factors: I—the ingot size, both thickness and width; 2—the length of the gas soak; and 3—the surface temperature. The first two factors determine the uniformity of the temperature distribution over the cross-section of an ingot. The third factor introduces the level of the heating of an ingot. The torque produced by an ingot being rolled is determined by the area of the metal displaced, its plasticity, and acceleration values. On the other hand, with shunt motors the torque is determined by the current. This can be assumed to be correct with only a small degree of error for compound motors with a relatively small effect of the series windings as long as the velocity is not regulated by weakening the field. Since the spread is relatively unimportant when compared to the width of an ingot and since it is also reduced several times during rolling by edging passes, the draft alone and not the area of the metal displaced may be taken into consideration with ingots of a similar size. It is therefore possible to determine the main features of the heating and drafting of an ingot by measuring the current and acceleration of the mill motor. After the acceleration has been taken into account, the amount of current will be an indication of how the motor responds to a heating and/or drafting practice and these practices can be adjusted in order to get the desired result. As peak currents are more likely when heavier ingots are rolled, the rolling of plate and slab ingots was investigated. Conditions prevailing when smaller ingots are rolled can be deduced from the results obtained on heavier ingots. All measurements were made when plain carbon grades under 0.15 pct C were rolled. The motor current, the voltage across the armature, and the rpm were recorded simultaneously on synchronized charts, Fig. 1, which moved with the speed of 6 in. per min. Each draft was recorded by a special observer. The rpm curve made it possible to establish the acceleration at any given moment. For purposes of correlation, the maximum current during a pass and the corresponding acceleration were used. The charts made it possible to establish the position of the roller&apos;s lever at any given moment as well as the total time of a pass. The slab ingots were divided into three groups (28x35, 28x45, and 27Mx53 in. ingots) and each group was investigated separately. Since they account for most of the current peaks, only flat passes were used for purposes of correlation, a total of 1373 having been investigated.

Jan 1, 1956

By S. R. Balajee, I. Iwasaki

The adsorption mechanism of corn starch and its derivatives at mineral-solution interfaces was investigated by the adsorption of cationic starch, unmodified corn starch, British Gum 9084, and anionic starch on quartz and hematite. The adsorption of these starches, which decreases in the order mentioned, is dependent on the balance between the magnitude of the electrostatic interaction and the magnitude of the hydrogen bonding. There exists a critical starch concentration for both optimum flotation and flocculation conditions of iron ores, which corresponds to a point where the starch adsorption reaches a saturation coverage. Flocculation occurs due to the adsorption of starch via electrostatic and hydrogen-bonding forces and by interparticle bridging as a result of the conformation of starch molecules at the interface. The depressant property of starches and starch derivatives in flotation&apos; and their flocculation char: acteristics in clarification and filtration2.3 have long been recognized on a wide variety of ores. The effectiveness of a starch as a depressant for iron minerals has been the subject of much investigation in recent years both in the amine flotation of siliceous gangue and in the anionic flotation of activated silica from iron ores. It has been reported that the depressant activity of starches and dextrins in the cationic flotation of quartz from hematite increases with molecular weight, branching, and number of hydroxyl groups, 1 and that the selectivity is affected by changing the configuration of starch molecules and the composition of its polar groups.4 ,5 The manner in which starches are solubilized was shown to exert a significant influence as a depressant in the anionic silica flotation, and a series of articles covering the practical aspects of flotation and flocculation have already been reported.618 Chemical modification of the starch structure, the pulp pH, the calcium ion, and the residual starch concentration were identified as some of the more important variables affecting the flotation behavior. In the flocculation of iron ores, it was noted that most starches flocculated suspensions of hematite in water but did not flocculate similar suspensions of quartz,9 and that an excessive use of starch restabilized the suspensions due presumably to protective action. 6 An admirable application of such an observation to practice may be cited in the selective flocculation and desliming in the anionic silica flotation of iron ores, which resulted in superior metallurgy and lower reagent cost. 10 From detailed adsorption measurements, Schulz&apos;and Cooke4 established that the adsorption of starches and their derivatives depended on the types of minerals and of starches, pH, and electrolytes present. Their adsorption data and the foregoing flotation and flocculation observations suggested that an electrical interaction between starches and charged mineral surfaces might be playing a role in their adsorption process. Adsorption of organic polymers, particularly of synthetic origin, at solid-liquid interfaces has been extensively studied in recent years,&apos; and it is realized that their adsorption mechanism is considerably more complex than that of simple ions or molecules. A polymer molecule possesses a number of functional groups, and the adsorption at a point may restrict the adsorbability of adjacent groups. The mechanism may be further complicated by the conformation of the polymer molecules which may exist as coiled spheres, helices, or extended chains as a result of intramolecular interactions among functional groups as well as intermolecular interactions with solvent molecules. The object of the present investigation was to examine the effect of the chemical modification on the adsorption characteristics of starches and starch products on quartz and hematite at several pH values, so that by correlating this information with flocculation and flotation results, adsorption mechanism of starches on mineral-solution interface may be elucidated. EXPERIMENTAL MATERIALS Quartz: St. Peter sand was screened at 35 mesh and the undersize was scrubbed and deslimed at a Fagergren cell. The deslimed sand was cleaned with 0.1 N hot hydrochloric acid and washed repeatedly with distilled water, For anuscript, measurementsl the -200-mesh fraction of the sand was ground dry in a porcelain mill for 3 hr. The specific surface of the finely ground quartz was

Jan 1, 1970

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-&apos; in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.&apos; The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964