Search Documents

By Lyall Zickrick

NUMEROUS brands of virgin pig lead are used in the manufacture of lead and lead-alloy cable sheath for commercial cables. In changing from one brand of pig lead to another a readjustment of press operating conditions is nearly always necessary. This is due largely to different flow characteristics, and some brands extrude at a much lower pressure than others; for example, copper-bearing lead requires much more pressure than a low-bismuth lead under the same operating conditions. With the modern type of lead press the extrusion practice in general differs very little. Molten lead at a temperature of 375° to 400° C. (710° to 750° F.) is cast in a water-cooled cylinder and allowed to cool or solidify into a slug for six to nine minutes. . This slug is forced into the die block and around the core tube through which the cable runs. The die block is held at an optimum temperature by means of gas flames, usually 175° to 225° C. (350° to 4.35° F.). Measurements of the tem¬perature of the cable sheath taken at the time of extrusion have covered a range of 190° to 225° C. (375° to 435° F.). According to Tammann, the rate of extrusion for a metal under constant pressure through a simple orifice is almost doubled for each 10° C. rise in temperature. Because of the irregularity of die-block construction, such a great increase is not obtained in lead-cable extrusion practice. To obtain more" definite information about the effect of small per¬centages of metals usually present as impurities in virgin pig lead, a series of compression tests were made covering several different brands of lead and various alloys. Since the usual temperature of the sheath is approxi¬mately 200.° C. as it emerges from the die block, these compression tests were all performed at 200° C. Five different brands of virgin pig lead were selected, as follows: Brand A: A desilverized western lead of very high purity. This lead contains neither copper nor bismuth. Brand B: A bismuth-free southeastern Missouri lead, usually con¬taining 0.05 to 0.08 per cent copper. Brand C: A copper-free mid-western desilverized lead of very good grade, usually containing around 0.06 to 0.10 per cent bismuth.

Jan 1, 1932

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By Joseph L. Jernegan

THE Whale Lode occurs in the main range of the Rocky Mountains, Park County, Colorado Territory, at Hall Valley. It has been opened up and worked to some extent by the Whale Mine, situated some 11,300 feet above the level of the sea. The mine, with 700 feet of the lode on either side of the discovery shaft, is the property of the Hall Valley Silver-Lead Mining and Smelting Company. The adjacent country rock is a compact, fine-grained gneiss ; its general strike is about north and south, dipping steeply to the west. In the immediate vicinity of the mine, the strata are very nearly vertical. The gneiss incloses numberless veins of a reddish granite, in which the feldspar largely predominates over the quartz and mica, the latter oftentimes being scarcely perceptible. As a general rule these granitic veins seem to more frequently follow the lines of stratification of the gneiss than otherwise. They are of varying width, some large, some small; the larger are from 5 to 6 feet wide. Gash veins of feldspar and quartz are also of very fre¬quent occurrence. The general trend of the lode is about northeast and southwest, intersecting the country rock at about an angle of 45° to its stratification. It dips to the northwest at an angle of 65°. I am unable to state accurately how far this lode has been traced upon the surface, but it is at least well known to extend entirely through the mountain upon which the mine is situated, and is traceable over the ridge by a hollow extending for some distance along the surface, in which the lode crops out. This hollow in the surface rock has probably been formed through decomposition of the vein matter by atmospherical influences. The width of the crevice is variable, generally between 5 and 10 feet; the pay vein varies from an inch, or less, to 36 inches. The vein is generally accompanied both on foot and hanging walls by a whitish, semi-decomposed rock, composed of quartz and decomposed feldspar, and in some places-where the process of decomposition has not reached as advanced a stage-a light-greenish or black mica. This rock, therefore, is in places composed of all the constituents of gneiss, and is undoubtedly nothing more or less than the same in a decomposed condition. It is often very strongly impregnated with iron pyrites, generally crystallized in minute cubes, and it is probably owing to the presence of this min-

Jan 1, 1875

By R. H. Wightman

THE following paper describes current mining practices of the Riverside Cement Co. at its Crestmore plant, Riverside, California. For a number of years the Riverside Cement Co. obtained its raw materials by surface quarry operations but after these deposits were exhausted for equipment available at that time, the company started underground mining. Mine workings were begun in 1927 to 1930 for the recovery of limestone by block-caving methods. GEOLOGY The bed of limestone that is being worked is a metamorphosed and recrystallized limestone, which is generally white in color and from medium to coarsely crystalline. This bed is fissured by water courses that vary from minute cracks to large areas. The bed has also been cracked by intrusions along the footwall and hanging wall. These walls are coarse-grained, gray, quartz granodiorite. The strike of the deposit is north and south and it dips to the east at an angle of approximately 50º. The bed is approximately 1700 ft. long, 270 ft. thick at right angles to the dip at the middle of the deposit and tapers to a thickness of approximately 100 ft. at each end. MINING METHODS The mine layout consists of four main levels with elevations as follows: 892 Collar of shaft. 800 Manway level used for ventilation, prospect purposes and as an entrance into the stopes. 700 Mining level where all material is extracted and on which are located the tapping grizzlies. This is the elevation from which all main cutoff stopes and undercutting work is started. 660 Haulage level where the limestone is drawn from transfer raises into the cars and is transported to the tipple by electric locomotives. 633 Level where all water is collected and which keeps the general water table below the working levels. A detailed description of the mine was given in U. S. Bureau of Mines Information Circular No. 6795, in June 1934. Current Block Development The first blocks to be caved were developed very much after the procedure followed in the copper mines of Arizona. This paper covers the ninth block to be caved. With a hard, tough rock like our limestone, it was found that some alterations in the development and control of draw in caving were necessary to secure better crushing effect and provide more safety for such secondary blasting as is required. Sequence of Block Development I. The fringes of the 800-ft. manway level are driven to confirm the diamond drill information and serve to determine the final location and development required for the block (Fig. I).

Jan 1, 1944

By William K. Antle

The successful application of ther mo compression lead bonding to semicondtctor or thin-film electronic devices depends on the establishment of the associated parameters. The quality of a thermocompression bond is primarily related to the process temperature and bonding force. A technique using the coelyicient of friction is presented that both reduces the time necessary for determining optimum parameter values and increases the accuracy of the results. Modern theories of the friction process are used to develop mathernatical expressions for shear and tensile bond strengths in terms of friction measurements. A further application of the pararneter-deterlnination technique concerns the measurement of surface contamination that may affect thermocompression bonding. In spite of the extensive use of thermocompression bonding, adequate methods for determining the bonding parameters have not been utilized. The quality of the weld depends on the temperature, force, and time used. There is a definite value or range of values for each parameter which assures an optimum weld. The process now generally used to obtain these values is to make several weld samples at each parametric setting, determine the mean pull strength, and relate the maximum consistent strength to optimum weld conditions. This could involve a very large number of test samples if a thorough search of each parameter were made. Experience and prior knowledge can reduce this number somewhat by limiting the investigation to a range known to contain the correct value, but the time and effort involved are still objectionable. The problems associated with thermocompression bonding of interconnecting leads to semiconductor or thin-film devices can be alleviated by the application of a new technique for establishing the process parameters. Obtaining the correct temperature, force, and duration to assure an optimum bond is accomplished by a simple measurement of the coefficient of friction. This approach increases the accuracy of parameter determination and greatly reduces the time necessary to complete the process. The approach made can be better understood by analyzing the principles of adhesion and friction on which thermocompression bonding depends. When two flat polished surfaces are placed together, the area of actual contact is much less than the apparent area determined by the over-all dimensions of the surface. This is because the microscopic surface is covered with projections which prevent uniform contact. Careful measurements of the electrical resistance across the contacting surfaces indicate the actual area may only be 1100,000 of the apparent area.' Because the actual contact area is small, extremely high pressure results from moderate force. This will produce deformation and plastic flow at contact points of the microscopic projections. The process will terminate in the creation of a large number of minute welds formed at extreme pressure and cold-worked to strong, hard bonds. Load removal will generally result in fracture of most of these microbonds because of the residual elastic stresses, unless the materials are soft. Friction between metals is due to the formation and

Jan 1, 1967

By I. R. Kramer

The stress associated with the high-dislocation layer at the surface of deformed aluminum crystals was measured by progressively polishing the specimen and determining the change in the initial flow stress when the specimen was reloaded. This surface stress increased linearly with strain in the Stage II and Stage III region. The depth to which the high-dislocation layer extends was found to be 0.0025 in. The influence of the surface layer on Stage I is discussed and it is shown that Stage I ends when, on the secondary slip system, the difference between the applied stress and the opposing stress due to the surface layer is equal to the critical resolved shear stress. In previous papers'-3 it was shown that the surface exerts a pronounced effect on the plastic-flow characteristics of metals. For fcc metals it was possible to increase the extent and decrease the slope of Stages I and II and decrease the work-hardening coefficient of Stage II by removing the surface of the specimen continuously during the deformation process.2,3 More recently,L it was shown that the activation energy for plastic deformation and the activated volume were also influenced by the surface. These changes were related to the existence of a high concentration of dislocations in the region near the surface of the deformed specimen and it was concluded' that the effective stress, T, acting on a dislocation was T = Ta-Ti-Ts [1] where 7, is the applied shear stress, Tj is the internal stress, and TS is the stress associated with the surface region containing the high concentration of dislocations. From Eq. [I] it is seen that the effective stress, 7, acting on a dislocation is a function of 7,. Therefore 7, becomes important in any description of the work-hardened state. In this paper the value of 7, as a function of strain and its variation with depth are reported for aluminum single crystals. In particular, it will be shown that the end of Stage I occurs when the net stress, 7, on the secondary slip system is equal to the critical resolved shear stress. To measure Ts, single crystals of aluminum were deformed in tension to various strains, whereupon the load was removed and a known amount of metal was removed by electrolytic polishing. The differ- ence between the final flow stress before the specimen was unloaded and the initial flow stress upon reloading is designated as ?Tp and is the decrease in the stress due to the removal of the surface layer in whole or in part. The value for Tp is taken equal to -Ts. EXPERIMENT PROCEDURE The details of the tensile apparatus, method of electrolytic polishing, and crystal preparation were the same as those used previously,1"3 The single crystals were 1/8 by 1/8 in. in cross section with a 3-in. gage length. The initial purity of the aluminum was 99.997 pet. The specimens were held in vacuo at temperatures 50°C below their melting points for 16 hr and furnace-cooled. Just prior to the application of the tensile stress the specimens were electrolytically polished to remove 0.004 in. from the thickness. This latter operation was conducted after the specimen was placed in the tensile apparatus. The tensile tests were conducted at a strain rate, i, of 10"5 sec-' and a temperature of 3°C. The aluminum crystals used for the determination of 7, are designated A1-3-12 and A1-116. The orientation of the various crystals used throughout the investigation is shown in Fig. 1. The ?Tp values for specimens A1-3-12 as a function of Ax were determined mainly at four strain levels, i.e., ? = 0.0217, 0.0381, 0.0593, and 0.075, where Ax is one half of the total reduction of the thickness after polishing and ? is the re-

Jan 1, 1965

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000' and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,' and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"'" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,'' and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By J. P. Denny

The constitution of the Ga-In system was determined by thermal methods. An experimentally determined metastable equilibrium line (an extension of the indium-rich liquidus) was obtained. The various alloys were studied metallographically using polished samples obtained by a casting method. These low melting alloys required a special dry-ice assembly to maintain a suitable temperature. RECENT interest in alloys that are liquid at room temperature has led to rather extensive investigation of gallium-base alloys. Widely distributed over the earth, gallium could be produced in substantially larger quantities than at present, if a significant demand existed.' One study' has established its presence in 12 out of 14 zinc blends, in all of 15 aluminum ores, in 4 out of 12 manganese ores, in 35 out of 91 iron ores, and in all of 7 magnetite ores. It occurs as a rule in minute amounts, however, leading to high extraction costs. Recent quotations run from $2.50 to $7.50 per g. During the course of the present investigation, portions of the system Ga-In have been redeter-mined, and the results of this study are presented herein. Thermal and metallographic methods have been employed. Lecoq de Boisbaudran, the discoverer of gallium, conducted the first investigation" on Ga-In alloys in 1885. The temperatures of incipient melting, and of completion of melting, were determined at four alloy compositions. In 1936, Hansen' constructed a eutec-tic-type phase diagram for the system Ga-In, based on . work. The existence of a Ga-In compound was regarded as improbable by Hansen, and subsequent investigations are in agreement. French, Saunders, and Ingle3 conducted a more complete study of the system in 1938, using thermal methods. Their phase diagram is a eutectic type, containing a unique concave-upward liquidus. The solid-solution range of gallium in indium was reported as 9.5 pct by weight, and that of indium as less than 1 pct, at the eutectic temperature. The eutectic composition, determined as being bracketed by the compositions showing a true horizontal at the eutectic temperature (16°C), was reported as 76 5-0.5 pct Ga and 24 i 0.5 pct In. Experimental Procedure The preparation of Ga-In alloys is simplified by the low melting points involved. Various compositions were prepared by melting in pyrex tubes, using a cover of distilled water or parafin to prevent the alloys from wetting the glass wall. In all cases, the melts were homogenized. by stirring. Where possible, both cooling and melting curves were determined. The extensive undercooling of gallium was found to prohibit a satisfactory cooling-curve analysis of gallium-rich alloys, however, and transition points on the gallium side of the eutectic could be determined only by melting curves. The inverse rate method of thermal analysis proved to be most satisfactory and was used to a great extent. Various heating and cooling rates were used, ranging from 0.2" to 5.0°C per min. Low temperature melting analyses were conducted within a constant temperature bath, maintained at about 70 °C. The alloys were solidified (under water or paraffin) within a pyrex tube, using dry ice; the tube was then sealed within a cold Dewar flask, the unit transferred into the constant temperature bath, and periodic temperature readings taken. The high temperature melting-curve determinations and all cooling-curve determinations were made in a vertical tube furnace. At near-eutectic compositions, the furnace was placed within a refrigerated room held at —20°C. Accordingly, the furnace on cooling approached —20°C asymptotically and permitted the determination of those phase transitions occurring below room temperatures. Temperatures were measured with a 30-gage iron-constantan thermocouple, immersed directly in the alloy. To prevent contamination of the melt, the leads and junction were coated with Lucite, applied by painting with a solution of Lucite in ethylene dichloride. Electromotive force measurements were made with a Leeds and Northrup precision potentiometer, type 8662. The couples were calibrated against the boiling point. of water and, at lower temperatures, against a calorimeter thermometer having a Bureau of Standards certificate. The melting points of gallium and indium used in the present investigation were determined as 29.-77° and 156.1°C, in good agreement with previously reported values of 29.78°C° and 156.4"C.' The spec-

Jan 1, 1953

By C. O. Brawner

Introduction The procedures used to design slopes in rock have only been developed over the past 10 years. Therefore, continued review and assessment of field experience by the publication of case studies is necessary to determine the accuracy of the theory and the application of the design techniques being used. Where failures have occurred, mine management should insist that the slides be 'back analyzed' to determine the shear strength parameters at failure. These values should be used for any pit design as they reflect site conditions more accurately than any other procedure. The previous papers have dealt with the basic concepts and factors that influence stability. To illustrate the application of these concepts in the study of practical stability problems, six ease studies have been selected for review. The examples include failure of tailings dams due to an earthquake, failure and redesign of a slope in overburden, review of failures of rock slopes, calculation of the amount of seepage into a pit and influence of the groundwater on stability, and the design of slopes for a proposed 2,500 ft. deep open pit mine. All but the first example are drawn from the authors personal experience. EXAMPLE 1 Failure of Tailings Dams Due to an Earthquake On March 28. 1965 a serious earthquake occurred in Chile with the epicenter located near the town of La Liqua, about 80 miles north of Santiago. The earthquake had a rating of 7 to 7.25 on the Richter scale. A record of the acceleration was taken at Santiago where a maximum horizontal acceleration of 0.18 g. was recorded. Many small mines are located in this region. Each of the mines provided impoundment storage for tailings with one to three dykes. As a result of the earthquake, most of the dams failed. The most serious failure involved two dams at El Cobre where more than 2,700,000 cu. yd. of tailings flowed into the valley, travelled over 7 miles in a few minutes, destroyed part of the town of El Cobre and killed more than 200 people. The Chilean government commissioned an investigation into the failures. A summary of the findings was published by Dobry and Alvare7 in 1967 (1). The location of the earthquake and the tailings dams which were investigated is shown

Jan 1, 1971

By K. Torssell, U. Lindborg

The kinetics of precipitation deoxidation is considered from a theoretical point of view. The size distribution and the total content of deoxidation products are estimated statistically as a function of time, taking into account Stokes and gradient collisions between the particles and separation at the top surface of the bath. The assumption is made that two particles coalesce into one larger particle as a result of a collision. General expressions are derived and calculations are carried out numerically for the case of silica particles in liquid iron. The analysis predicts a three-stage behavior for the removal of oxygen, an incubation stage, a stage of rapid separation, and a slow final stage where the content approaches the equilibrium value. The agreement with experimentally determined size distributions and deoxidation times is considered to be good. A quantitative estimation of such growth mechanisms as diffusion from the melt and redistribution of oxygen from small particles to large ones shows that these latter mechanisms cannot explain the experimentally observed gvowth of inclusions. This also indicates that collisions provide the important growth mechanism. OXIDE inclusions precipitate when a deoxidizer like silicon or aluminum is added to a steel bath. The inclusions grow and the large particles tend to separate from the bath. For each type of oxide the growth determines the sizes of the final inclusions as well as the total inclusion content of the steel. The mechanism of growth is controversial, however. It has been suggested that an inclusion grows principally by diffusion of atoms through the melt to the inclusion particle or principally by collisions and coalescence with other inclusions. Diffusion growth is always present to some extent but recent experiments and calculations by Torssell,' Kniippel et 'a1.,2 Sano et al. and Miya-shita4 indicate that collisions may be more important than previously realized. A detailed analysis has so far been lacking. The present paper is a quantitative, statistical analysis of the growth and separation of inclusions and is based on a collision theory. Nuclea-tion is not considered. The numerical estimates are based on the experimental conditions of Torssell's' investigation and comparisons are made with his observations. Torssell' studied the growth and separation of silica particles in liquid iron. Samples were taken from a 0.6 kg iron bath at various times after the addition of silicon. By a particle-counting technique developed by Bergh and Lindber~the size distribution of the inclu- sions was determined. The number of particles at the first sampling, 10 sec after silicon addition, was of the order of 3 x lo7 to 10' per cu cm, the largest particles having a radius of 2 to 4 pm. The volume fraction was 0.001 to 0.004; i.e., the dispersion was very dilute. During subsequent holding the largest particles increased their radius by a factor of 10 after about a minute, and the whole size distribution was displaced toward larger values. These results were obtained with allowance for precipitation of the equilibrium concentration of oxygen during solidification. The bath contained less than 0.01 pct of C. Figs. 1 and 2 show the typical appearance of the inclusions. Most particles are very closely spherical and appear to have been liquid or semiliquid in the melt. The observed number of inclusions, about 5x 10' per cu cm, is of the same order of magnitude as found by ~er~h.' This is a large value. It follows that the diffusion distances are very short and that the precipitation

Jan 1, 1969

By G. Donald Emigh

Nothing is more important to life-plant and animal-than phosphate. Its compounds are essential to the energy functions of all living systems and for the formation of bones and teeth. Animals get their phosphate from eating plants and other animals, or domestically from feed supplements. Plants get their phosphate from the soil. Man's most important use of phosphate is for fertilizer; however, he is also a heavy user of many industrial phosphate chemicals. Phosphate occurs in all igneous and sedimentary rocks, and in all fresh and saltwater. The average content in rocks is 0.1 to 0.2% P2O5, as documented recently by McKelvey (1973). About 200 minerals contain more than 1 % P,O,. However, the important one in igneous rocks is fluorapatite, (Ca,(PO,) ,F) containing about 42% P,O, and 3.8% F,; in sedimentary rocks the one important mineral is francolite, a carbonate fluorapatite containing up to 2% molecular CO,. Both are in the apatite family of minerals. The mineralogy of phosphate minerals was reviewed recently by Altschuler (1973). Although phosphate occurs in nearly all rocks, economic recovery is limited to deposits where natural concentration of the phosphate mineral has occurred. Occasionally natural concentration is great enough that the material can be used as mined; generally, however, the ore is low grade and must be concentrated.

Jan 1, 1975

By C. H. Samans, G. F. Tisinai, J. K. Stanley

The times at which the first detectable amount of a phase forms at temperatures between 900° and 1800°F were determined. Both X-ray diffraction and metallography were used to detect a in highly strained filings; metallography alone to detect it in annealed bulk samples of six different types of stainless steels. The a phase was found to form in accordance with the C-type reaction curve in both austenitic and ferritic alloys. In filings of types 304, 347, and 446, a formed in a few hours, and in types 316, 309, and 310, it formed in a matter of minutes at temperatures corresponding to the knee of the C-curve. Only in the bulk type 309 steel, after 500 hr, and in the bulk type 310 steel, after as short a time as 25 hr at temperature, was n detected; in both instances at approximately the same optimum temperature as in the filings. The annealing temperature affected a phase nucleation only for the filings of type 304 and 347 steels, and for the bulk samples of type 309 and 310 steels. KNOWLEDGE of both the rate of nucleation and the rate of growth of the new phase is required for a complete description of metallurgical rate phenomena. However, data on the time for nucleation alone may frequently be useful in evaluating the tendency of commercial stainlcss steels to form s under various conditions. Very little correlated information of this type is available in the literature. Shortsleeve and Nicholson' indicate that s forms in ferritic 24, 27 and 30 pet Cr steels according to a C-type of reaction curve, and Emmanuel's' data for austenitic type 310 steel also suggest this type of solid state reaction. In addition, significant, though fragmentary, information has been given by Binder, Dulis and Smith,4 Payson and Savage,.; Guarneri, Miller, and Vawter,8 rerichs and Clark,7 Wilder,5 Lismer, Pryce, and Andrews,' Smith, Dulis, and Link,10 Dulis, Smith, and Houston," and Henry, Cordovi, and Fischer." The bearing of these data on this work is covered in the discussion. The purpose of this paper is to present such correlated data on s formation in AISI type 304 (18 pct Cr-8 pet Ni), 347 (18 pet Cr-10 pet Ni-Cb), 316 (18 pet Cr-12 pet Ni-2 pet Mo), 309 (25 pet Cr-12 pet Ni), 310 (25 pet Cr-20 pet Ni), and 446 (27 pet Cr) stainless steels. Materials and Test Methods X-ray diffraction and metallographic methods were used to determine the first appearance of the s phase in cold worked filings and in annealed bulk samples of seven steels, under various combinations of time and temperature. The rate of growth of the s particles was not determined. Commercial heats of six AISI steels and a low carbon laboratory experimental heat containing about 28 pet Cr were studied. Analyses are given in Table I. Because cold work greatly accelerates the nucleation of s particles, the relative rates of s nucleation in mechanically strained samples, i.e., filings through 120 mesh, were determined for direct comparison with those in annealed bulk alloys of the same composition.

Jan 1, 1957

By Wm. Reuben Webster

Brass is an alloy of copper and zinc. The brass containing 70 per cent copper and brasses (using this term to denote all useful 30 per cent zinc. Fig. 3 shows the effect of proportions of the two constituents) are the annealing at various temperatures on the most valuable and widely employed of all same alloy. This effect is somewhat modi- nonferrous alloys, because of their high resistance to ordinary corrosive agencies and the very wide range of properties that may be imparted to them by variations in the proportions of the constituents and by variations in mechanical treatment and heat-treatment. Fig. I shows the normal physical properties, as determined by standard tensile tests, of the series when in the annealed condition. Fig. 2 shows the effect of varying amounts of cold-working on an almost pure fied by the degree of cold-working to which a brass has been subjected, as shown by Fig. 4. A fourth test, which is empirical, has been found useful because of its simplicity —the hot hammer test. Samples 1/2 in. in diameter and 3/4 in. long are placed in a suitable furnace. These are withdrawn one at a time. at successively higher temperatures and are subjected to the blow of a drop hammer weighing 50 lb. with a drop of 4 ft. The percentages of reduction in length of the cylinders are plotted against temperatures and give a camparative measure of plasticity at different temperatures. The results of this test on several

Jan 1, 1942

By Wm. Reuben Webster

Brass is an alloy of copper and zinc. The brass containing 70 per cent copper and brasses (using this term to denote all useful 30 per cent zinc. Fig. 3 shows the effect of proportions of the two constituents) are the annealing at various temperatures on the most valuable and widely employed of all same alloy. This effect is somewhat modi- nonferrous alloys, because of their high resistance to ordinary corrosive agencies and the very wide range of properties that may be imparted to them by variations in the proportions of the constituents and by variations in mechanical treatment and heat-treatment. Fig. I shows the normal physical properties, as determined by standard tensile tests, of the series when in the annealed condition. Fig. 2 shows the effect of varying amounts of cold-working on an almost pure fied by the degree of cold-working to which a brass has been subjected, as shown by Fig. 4. A fourth test, which is empirical, has been found useful because of its simplicity —the hot hammer test. Samples 1/2 in. in diameter and 3/4 in. long are placed in a suitable furnace. These are withdrawn one at a time. at successively higher temperatures and are subjected to the blow of a drop hammer weighing 50 lb. with a drop of 4 ft. The percentages of reduction in length of the cylinders are plotted against temperatures and give a camparative measure of plasticity at different temperatures. The results of this test on several

Jan 1, 1942

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today's most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.'.' The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,' but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.' The imbibition characteristics of

Jan 1, 1958

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By A. H. Daane, J. J. Hanak, F. H. Spedding

IN the study of the rare earths at the authors' laboratory, methods have been devised for preparing pure rare earths and many of their properties'- have been determined. Very little information is found in the literature on the properties of europium metal, which is the scarcest of the naturally occurring rare earths. Since we have recently prepared europium in appreciable quantities, we are in a position to describe the method of preparation and some of the properties of this metal. Metallic europium was first prepared by Klemm and Bommera who heated a mixture of potassium and EuC1, in vacuo, and obtained a mixture of europium metal and KC1. Trombe4 electrolyzed a molten salt bath containing NaC1, KC1 and EuC1, and collected the europium in a molten cadmium electrode as a cadmium alloy. The cadmium was subsequently removed by distillation but the properties of the residue indicate that pure europium was not obtained. McCoy attempted to prepare europium by distilling mercury from europium amalgam, but the stability of the Eu-Hg intermetallic compounds prevented a complete separation of the two elements. The preparation of very pure europium was suggested by previous work in this laboratory1,4 in which ytterbium and samarium were prepared by heating the respective sesquioxides with lanthanum metal turnings to 1450°C in vacuo and distilling ytterbium and samarium from the mixtures. Subsequently, small test experiments showed that europium also could be prepared by this method. A more detailed version of this method was used in the work described in this paper. Klemm and Bommer3 found by X-ray analysis that the metal had a body-centered cubic (bcc) structure with a lattice constant a, = 4.582 ± 0.00A (converted from kX units), with a bulk density of 5.30 g per cu cm. They found europium to be weakly ferromagnetic. Spedding, et al,7 found a,, to be 4.606 ± 0.001A. Barrett' showed that the bcc structure persists throughout the temperature range 5 to 3000K with a, at 5, 78, and 300°K being 4.551 ± 0.003, 4.551 ± 0.004 and 4.577 ± 0.001A, respectively. Trombe1 described europium as being iron gray, malleable, about as hard as neodymium and not attacked by cold water. He estimated the melting point to be between 1100 and 1200°C. Previous work in this laboratory indicated that the pure metal corrodes rapidly in air and reacts with cold

Jan 1, 1959

By D. H. Thompson, A. W. Tracy

Season-cracking is a type of failure of brass that results from the simultaneous effect of stress and certain corrodants. The object of this paper is to present data that will aid in a more complete understanding of the mechanism of season-cracking and related phenomena. Results presented show that certain high copper alloys are susceptible to season-cracking or stress-corrosion cracking, and possible explanations are discussed. Starting at least as far back as 1906, many papers have been devoted to this subject but the symposium1 held in Philadelphia in 1944 is the richest source of information. In order to study season-cracking, several of the many variables were held constant so as to learn the effects of others. Season-cracking is generally understood to refer to the corrosion cracking of brass having internal stresses;²,³ it is a special case of the general stress-corrosion cracking. Inasmuch as applied stresses are more readily produced and controlled, they were used exclusively in this research and the resulting phenomenon must he called stress-corrosion cracking.²,³ Only constant tensile stresses were used. The agents believed to be most frequently responsible for season-cracking are ammonia. amines and compounds containing then]. Both moisture and oxygen also appear to he necessary. Therefore, an atmosphere containing ammonia, water-vapor and air was selected for these tests. Briefly, the work consisted of exposing sheet metal specimens, having a reduced section ¼ by 0.050 in., of copper-base alloys to the effect of static tensile stresses between 5,000 and 20,000 psi and simultaneous contact with a. continuously renewed atmosphere containing 80 pct air, 16 pct ammonia and 4 pct water vapor at 35°C. The gas mixture and the speci- mens were maintained above the dew-point. The time-to-failure in minutes was the primary measure of results. In order to limit the experiment to finite time, it was considered that a specimen which had neither failed nor undergone microscopically detectable cracking in 40,000 min. (4 weeks) while under a stress of 10,000 psi or more could be considered immune to cracking. This is merely a convenient limit and is not to be considered proof of immunity. Supplementary tests in the absence of stress using weight loss or microscopical appearance as measures of attack were made. Apparatus The apparatus used in this research is shown in Fig 1. To facilitate the description it may conveniently be divided into six parts: stress-producing units, test chamber, gas train, electrical controls, timers and gas analysis device. A stress-producing unit is shown in an exploded view at the left in Fig 2. At the right is an assembled unit with a specimen in place in the lower portion; it is this part that remains in the ammonia atmosphere during a test. The upper part contains a spring, a central threaded rod, a large nut and necessary washers, pins, and so forth. Stress is produced in the specimen by screwing down the top nut against the spring, thus putting a tensile load on the central rod and so on the specimen. The wrench that turns the nut by extending through the upper cap, is seen at the upper right of the figure. The magnitude of the load is gauged by measuring from the pin that extends through the side of the tube, to a fixed point on the large flange. Measurement is made with a vernier beam caliper, shown at the right of the figure. The necessary spring compression to give a desired stress is calculated from the calibration curve of the spring and the dimensions of the specimen. The test chamber, center Fig 1, consists of a thermally insulated steel box 32 in. long by 10 in. high by 7 in. wide. A horizontal baffle reaching nearly to each end divides the chamber equally. Below this baffle are inlets for air and ammonia, a heating coil and a fan. Thus the gases are warmed and mixed in the lower level and flow past the specimens in the upper level. A thermo-regulator and thermometer project into the upper space. The top is pierced by 12 ports flanked by 3/8 in. threaded studs. A test starts when a port is opened and a unit containing a stressed specimen is thrust through it and bolted down against a neoprene gasket. The test chamber is held at 35°C. The gas train, right rear Fig 1, carries ammonia and air continuously to the test chamber. Tank ammonia passes through two reducing valves, a needle valve, a flow meter and into the test chamber. The air from either the plant compressor or a small laboratory compressor passes through wool towers and flow controls to the flow-meter. It then bubbles through water at 34°C and through a heated line to the test chamber. Electrical controls, left rear, Fig 1, provide rectifiers and mercury relays for the test-chamber and humidifier-heating-control circuits and outlets for

Jan 1, 1950