Search Documents

By A. Lubinski, C. R. Stewart, K. A. Blenkarn

Storage porosity has been considered one of the important pore geometry characteristics of heterogeneous-porosity limestones. Storage pores are only containers for fluids, in contrast to flow channel pores which both contain fluids and provide continuity for fluid flow. The concept of another geometry characteristic, "poro-striction", is presented as a second pertinent variable in describing limestone pore space. In simple terms, poro-striction is a measure of the flow resistance between storage and flow channel pores. Alternating-flow core-testing theory provides flow relationships which can be used to divide the pore space of heterogeneous-porosity media into flow channel and storage pores and to measure the "porostriction" of the latter. Experimental application of this theory to naturally occurring heterogeneous limestones shows that "porostriction" and the ratio of storage to flow channel pores can be estimated. Porostriction and porosity ratio are microscopic characteristics which should influence oil-recovery efficiencies during certain types of displacement processes. A knowledge of pore geometry should be valuable in designing or selecting the most effective oil-recovery process for heterogeneous limestones containing storage porosity. INTRODUCTION The primary and secondary recovery of oil from limestone (carbonate) reservoirs has been and will continue to be a major source of the world's supply of petroleum. Oil recovery from this type of formation is strongly influenced by the size, shape and arrangement of the pore spaces which hold the formation fluids. Therefore, it is expected that better knowledge of pore geometry would lead to design of more effective recovery processes. The concept of storage and flow channel pores has been presented as an important characteristic of limestone porosity.1 In this concept, storage pores are only containers for fluids, whereas flow channel pores are those pores which both contain and transmit the fluids. The work reported herein involves the concept of an additional pore characteristic called "porostriction". This characteristic can be visualized as the flow resistance between the storage and flow channel pores. This resistance is an important pore geometry characteristic because it determines how easily gas and oil can replenish fluids removed from the flow channel pores. Fatt and co-workers at the U. of California have studied the effect of storage porosity and a factor similar to porostriction on transient-flow response of models of porous media during a pressure build-up or drawdown test.55 These models consisted of porous sandstone cores with artificially simulated storage pores. It is the purpose of this paper to describe tests which permit the storage porosity and porostriction of actual reservoir core samples to be estimated. The tests used for this purpose involved not transient tests but, rather, an alternating-flow technique in which pressure and flow are varied according to a sine-wave relationship. This technique may offer advantages over transient methods. THE POROSTRICTION CONCEPT Before discussing alternating-flow (A.F.) tests in core samples, it is necessary to define the porostriction parameter. For this purpose attention is focused upon an elemental volume v representative of a porous medium having both flow channel pores and restricted-access storage pores. For such an elemental volume, it is considered that the storage porosity is combined to form a single pore and that the access into the storage porosity may be represented by a single capillary tube connecting the single pore to the flow channels of the elemental volume. Let the radius of the capillary tube be designated as Rc and its length as L,. When fluid flows into or out of the pore, the following equation (Poiseuille's law) relates flow rate q to pressure drop p, and the physical characteristics of the tube and the fluid of viscosity jx.

By G. A. Beske, P. Hilsch, J. Wulff

The effects of the growth precipitates on the su-perconduching properties of an Al- 15 al. pel Zu alloy have been studied using magneization, transition lem-perature, and residual resistivity measurements. Aging at 230C for 1/2 to 11 he produces an increase in Hfp, Ike field of first penetration, and tut increase in trapped flux. The upper critical field, Hc2 remains constant for such aging tunes. Aging at 200°C produces a decrease in Hfp and an increase in trapped flux. The transition temperature remains constant at Tc - 1.227° ± 0.02°K for aging at 220°C for tims of from 1/2 to 10 hr, and for aging at 200°C it remains constant at Tc. = 1.18° i 0.02°K for times from 1/2 hv to 26 hr. The observed behavior indicates that the superconducting matrix when aged at 220°C behaves tike a type U su-perconducior, but when aged at 200°C behares like a type I superconductor. The magnetization changes after aging can be attributed to the growth and clutnge in distribution of the precipitate in a matrix of fixed composition. IT has been realized for some time that the superconducting properties of alloys are highly structure-sensitive. This is evident in the work of Mould and Mapother1 who examined the properties of an aluminum alloy. Precipitation effects have also been briefly mentioned in other studies.2-4 Bonnin and coworkers5 have observed a sharp inc rease in trapped flux in an A1-Mg alloy when the residual resistivity reaches a value that indicates it is a type II superconductor. Recently Blanc, Goodman, and Nemoz5p have reported on precipitation effects in A1-Ag alloys. Detailed studies of precipitation in Pb-Sn and Pb-Cd alloys made by Livingston6 serve to show that the upper critical fields are enhanced by quenched-in solute. Furthermore. at various stages in the precipitation process? the upper critical field is determined largely by the remanent solute. The observed magnetic hysteresis and trapped flux in such alloys result from the interaction between precipitate and the flux filaments in the mixed state. The flux trapping appears to depend largely on the precipitate distribution and is greater if the superconductor is type II than if it is type I. To examine the effect of precipitation in another alloy system, particularly one in which the composition of the superconducting phase does not change significantly during the course of precipitation, the Al-Zn system seems interesting, especially in view of the transition temperature and resistivity studies of Chiou and seraphim.' Furthermore, the recent detailed electron-microscope studies of an Al-Zn alloy by Richards and Garwood8 provide a guide for relating superconducting properties to changes in structure. For these reasons, magnetization, transition temperature, and residual resistivity measurements for varying times of heat treatment at two temperatures were made with a -15 at. pct Al-Zn alloy. The results are reported in this paper. I) EXPERIMENTAL The alloy used was prepared by Cominco Products Inc. from 99.9999 A1 and 99.999 Zn. It was chill-cast, swaged, and drawn to 0.125-in.-diam rod. The analyzed composition was 15.6 at. pct Zn (31.1 wt pct). A jeweler's saw was used to cut the 0.125-in.-diam rod into the 0.875-in. lengths needed for magnetization measurements. The ends of the cylinders were slightly beveled to remove the sharp edges. A portion of the original 0.125-in.-diam rod was drawn into 0.010-in.-diam wire and used for transition temperature measurements. Specimens were suspended from wires within a vertical furnace during heat treatment. All were homogenized at 500°C for a minimum of 3 days and subsequently solutionized for times in excess of 6 hr. The solutionizing temperature was held constant to +3°C. Individual specimens were homogenized, quenched, and aged several times and no effects indicating loss of zinc were noted. The suspended specimens were quenched by cutting the wires and allowing the specimens to fall into a silicone oil bath held at the aging temperature. They were then isothermally transforked by aging in the same bath used for quenching. After aging for the required time (approximately 10 min aging was necessary before the upper critical field reached a fixed value), they were briefly (1 to 2 sec) dipped into an acetone bath at room temperature to remove adherent oil and then immediately transferred to liquid nitrogen where they remained until inserted into the helium bath (usually within an hour). The temperature of the aging bath was held constant to +3°C for longer aging times. The cryostat used for the measurement of superconducting properties consisted of outer and inner dewars for liquid nitrogen and liquid helium, Stokes 6-in. booster diffusion pump and Stokes Model 212 mechanical pump, temperature controller to measure and control the temperature of the helium bath, and a superconducting solenoid with inserted search coils to provide the magnetic field and measure the magnetic moment of the specimens. A schematic diagram of the cryostat is shown in Fig. 1. An ultimate temperature of 0.85°K was reached with this apparatus. The temperature controller used is similar to the one described by Blake and chase.' A 0.5 pct Allen-Bradley carbon resistor and a nichronle heater (200

Jan 1, 1968

By K. R. Price, M. Gauna

A high seam geologic condition exists at Jim Walter Resources No. 4 mine that requires immediate rib support after a continuous miner cuts a place. High seam mining heights are typically 2.4 to 2.6 m (8 to 9 ft) and a thick rock layer is present in the upper portion of the coal rib side. The 610-m (2000 ft) mining depth at No. 4 mine induces horizontal rib line movement after excavating an entry. Horizontal rib movement greater than 305 mm (12 in.) have been noted. When lateral movement occurs in the high seam areas, the thick rock layer, and the coal above the rock layer, become fractured and tend to roll into the entry. If not adequately supported, large rib rolls develop in the place being bolted as well as in previously mined areas that endanger men and equipment. To control this, rib support must be installed in the roof bolting operation as the bolting crew works toward the face. A rib control system has been developed for this high seam mining condition using a mechanical anchor bolt placed at an angle in the rib and installed with a modified Fletcher DDM-15 bolting machine. More than 120 km (75 miles) of entry have been supported with angle rib bolts. These angle bolts constitute 43% to 60% of the total roof and rib bolt footage in the high seam portions of No. 4 mine. The angle rib bolting system has proven safer, more effective, and more efficient than the earlier support method using bolts installed horizontally into the rib. No rib roll accidents have occurred since the angle drill bolting machines were placed in service in 1981. By securing the broken rib material with an angle bolt anchored above the coal pillar, a more effective means of rib control is achieved. Angle rib bolting does not interfere with continuous miner productivity. In addition, bolting crews are now reduced from three to two people. Total drilling supply costs are about 60% the previous cost, when compared to the previous support method using horizontal rib bolts:

Jan 1, 1985

By V. Koump, T. F. Perzak, R. G. Olsson

The rate of dissolution of recrystallized alumina in molten iron oxide in equilibrium with iron at 1450°C was studied by rotating alumina disks in the melt. The samples were rotated from 1 to 12 min at speeds from 54 to 3270 rpm. It is concluded from the experimental results that the process is limited by diffusion in the liquid boundary layer. The interdiffusion coefficient for the dissolution of alumina disks in pure molten iron oxide was estimated to be about 3 xl0-5= sq cm per sec. THE erosion of refractory materials is of considerable importance in iron- and steelmaking processes. Since many refractories contain alumina, this investigation was undertaken to develop a further understanding of the erosion mechanism. Shurygin et al.1-3 have investigated the rate of dissolution of alumina in molten silicates and molten fluorides by rotating alumina disks in various melts. The rates were reported to be limited by diffusion in the liquid boundary layer. In the present investigation the rate of dissolution of alumina in molten iron oxide in equilibrium with iron was studied in a similar manner; alumina disks were rotated at different speeds in molten iron oxide at 1450°C. The relationship between the rate of dissolution of the flat surface of the disk and the speed of rotation was used to determine whether the process is limited by diffusion in the liquid boundary layer or by some chemical reaction mechanism. APPARATUS AND EXPERIMENTAL PROCEDURE A schematic diagram of the experimental apparatus is shown in Fig. 1. The iron oxide melts were contained in 2-in.-diam high-purity iron crucibles that were centered in a cylindrical graphite susceptor. Prior to each sequence of experiments, sufficient reagent-grade ferric oxide was added to a crucible to form approximately 350 g of molten iron oxide; the depth of the melt was about 11/2 in. To prevent excessive erosion of the crucible, about 70 pct of the required iron was added to the crucible in the form of iron powder. The mixture was melted in an atmosphere of purified argon by induction heating with a 250-kc generator. After the oxide was molten, a Pt/Pt-10 pct Rh thermocouple at the exterior of the crucible was calibrated against an iron-sheathed thermocouple immersed in the melt and was thereafter used to regulate the melt temperature. All experiments were conducted at 1450°C with a probable error of 10°C. The alumina disks were constructed from pure re-crystallized alumina having a density of 3.7 g per cu cm (porosity approximately 6 pct). For each disk sample a 1-cm-diam alumina cylinder of known length (0.9 to 1.0 cm) was cemented into a ground seat at the end of a 1.27-cm-OD centerless ground alumina tube. The ends of the tube and cylinder were flush and served as the disk surface. When mounted in the apparatus the alumina tube was guided by tungsten carbide bearings and rotated by a variable-speed motor. The bearing and drive assembly could be raised and lowered in order to allow the sample to be quickly moved in and out of the melt. At the start of an experiment, a sample was preheated for several minutes directly above the melt, and then immersed in the middle of the melt to a depth of a in. and rotated for 1 to 12 min at speeds of 64 to 3270 rpm. The speed of rotation was measured by a hand tachometer. At the start and completion of each experiment, a melt sample was withdrawn with a cold copper rod and the alumina content was determined by chemical analysis. During individual experiments the alumina concentration of the melt changed by the order of 0.25 wt pct. Average melt compositions for individual experiments were used in the subsequent computations and were in the range between 0.12 and 4.3 wt pct alumina. The extent of dissolution was determined by sectioning the end of the sample and measuring the final length of the alumina cylinder with a microscope. Since the exposed end of the cylinder, i.e., the disk surface, was etched in a manner characteristic of this geometry, a number of measurements were made on

Jan 1, 1969

By Baxter C. Madden

Stress corrosion is defined and certain examples are illustrated. A number of test methods, to determine the resistance of materials to stress corrosion, are being developed at Wright Field. The criterion as to the validity of a method is stated. Three types of specimens and the method of stressing each type are described. Five different corrosive conditions are set forth. The results of tests to date, although too few for any general conclusions to be arrived at, are presented. The program for the continuation of the investigation is indicated. A bibliography is included. The development of the method of loading a cantilever-type specimen, so that a nearly constant stress at a large deflection may be realized, is presented as Appendix I.

Jan 1, 1945

APPROXIMATELY 26 percent of the total ore production to date from the largest single deposit of copper-bearing material in the world was mined during the war years, 1942 to 1945, at Chile Exporation Company's great open-pit mine at Chuquicamata, Chile. About 18 percent of the total waste removed during the life of the mine was handled in the same period. The total of ore and waste represents approximately 24 percent of the total material that has been excavated from the pit. This is more than was removed in the first fourteen years of operation from 1914 through 1927. The pit at Chuquicamata is 17/8 miles long, 1/2 mile wide, and has a present vertical extent of 817 ft between the top of the highest bench and the lowest bench being worked. However, when

Jan 1, 1948

By Elmer W. Pehrson

Minerals have played a prominent role in the affairs of man and nations since time immemorial but with the advent of the industrial revolution, expanding use of the products of the mineral kingdom became synonymous with the material progress of mankind. Individuals and business groups have recognized this fact so have been aggressive in searching for and utilizing mineral resources, with notable success. Indeed, their achievements are primarily responsible for the present Machine Age. On the other hand, until recently the body politic has failed to grasp fully the essentiality of minerals although, at times, access to mineral supplies has been an important factor in the political maneuvers of nations. This chapter is concerned primarily with the broader political and economic relationships of mineral resources to the world economy, and with the internal and external actions of nations in the field of minerals. Many factors that condition the mineral economy of regions and the world as a whole, influence the internal and external affairs of individual nations. The more important of these are: 1. The nature of man's dependence on minerals. 2. The problems resulting from the unique characteristics of mineral occurrence. 3. Geopolitical concepts. 4. Minerals and world power. Actions of individual nations affecting their mineral economy seek two basic objectives : 1. Attainment and maintenance of prosperity. 2. Military security. Other objectives may be cited but on careful analysis they become integral parts or extreme phases of the two points noted above. For example, the twentieth century aggressions of the USSR, Germany, Italy, and Japan might be considered as direct bids for world power but they also can be interpreted as exaggerated or mistaken efforts toward military security and peacetime prosperity. Similarly, trade barriers, nationalization of industries, foreign exchange manipulations, taxation, monopolistic prac-

Jan 1, 1959

By J. P. Morgan, J. R. Dawson

A review of Jones & Laughlin's Vesta coal preparation plant flowsheet in 1959 indicated that, of the three sizes making up the company's metallurgical product, the -48-mesh fraction offered the greatest potential for improvement. Efforts to improve quality and yield were directed toward the use of froth flotation. After laboratory and plant tests were completed, it was decided that treatment of the entire -@-mesh fraction of the coal mix by flotation was a significant step forward in providing better coal quality and recovery. Reduction of ash in the metallurgical coal from 6.75 to 6.25% provided material savings at the coal washer, coke plant and blast furnace. The Vesta preparation plant of the Jones & Laughlin Steel Corp. is located on the Monongahela River, eight miles south of Brownsville, Pa. This plant is capable of cleaning 2400 tph of a mixture of Pittsburgh seam high volatile coals from the Vesta and Shannopin mines to produce a metallurgical coal of 6.75% ash and a steam coal containing 14% ash. Heavy media vessels are utilized to upgrade the coarse coal while launders and tables handle the -1/4-in. fraction of the raw coal feed. Cleaned -1/4-in. coal goes to boot classifiers where the 48 mesh material settles and is removed by bucket elevators. This 1/4x48 mesh material is then sent to centrifugal dryers for dewatering. As designed, the -48 mesh fraction overflows the boot as a 7 to 8% solids slurry and is recovered by cyclones and a thickener and then dewatered by filtration. The products of the heavy media circuit, the launder-table-boot-dryer circuit and the cyclone-thickener-filter circuit, are combined to constitute the shipped metallurgical coal. The Vesta-Shannopin mix is combined at Jones & Laughlin's Pittsburgh and Aliquippa Works with purchased low and medium volatile coals for the production of metallurgical coke. A review of the preparation plant flowsheet in 1959 indicated that of the three sizes making up the metallurgical product, the -48-mesh fraction, containing 16.7% ash, offered the greatest potential for improvement of coal quality. This fraction was considered low, averaging 55%, while the rejects averaged only 33% ash. It was evident that while the boot overflow fraction represented only 6% of the product mix, a reduction in ash to 6 or 7% would reduce the ash of the metallurgical coal by 0.5%. The original plant flowsheet handling the boot overflow (Fig. 1) consisted of ten 14-in. cyclones treating 70% of the overflow and producing a 48x150-mesh underflow and a -150-mesh overflow. The cyclone overflow was combined with the remaining 30% of the boot overflow to constitute the feed to a 150-ft thickener. The cyclone underflow and the 48x325-mesh thickener underflow were fed to vacuum disk filters for dewatering prior to combination with the coarse metallurgical coal. The thickener overflow stream containing the -325-mesh material was split, 40% being recycled directly to the plant water system and 60% being flocculated and clarified in an 85-ft thickener. The underflow of this thickener was pumped to waste. Efforts to improve quality and yield on the -48-mesh coal were directed toward the use of froth flotation early in the investigation. A review of the fine coal flowsheet indicated that three streams should be considered for treatment by froth flotation. These were the -325-mesh thickener overflow, the -150-mesh cyclone overflow and the -48-mesh boot overflow. Flotation of the thickener overflow was considered basically to improve recovery by upgrading the reject stream so that it could be fed to the filters along with the thickener and cyclone underflows. The overflow from the thickener contained 3.7% solids and had an ash analysis of 33%. Flotation of the cyclone overflow and boot overflow were considered to upgrade coal quality as well as yield. Treatment of the cyclone overflow, a 5.4% solids slurry averaging 27% ash, would eliminate the coal thickener and provide a feed of flotation concentrate and cyclone underflow to the filters. Treatment of the boot overflow would eliminate both the cyclones and thickener and feed only flotation concentrates to the filters. Flotation feed in this

Jan 1, 1962

By ALFRED T. BARR

In certain areas of the New Cornelia pit, considerable secondary blasting is necessary to reduce oversized boulders, formed from primary blasting, to pieces which will pass the 41/2-cu yd dippers on the shovels. Some of the boulders are 'dobied, but when time permits they are blockholed and blasted. In most instances one hole drilled to a depth of 2 to 3 ft and blasted with 1/3 to 1/2 of a stick of powder will break a boulder satisfactorily. Blockholing is normally done by using a jackhammer of the 55-lb class, 1-in. round drill steel, and detachable steel bits, 2-in. gauge when new. A bit change is usually made after the completion of each hole. The use of light drilling equipment in blockholing is desirable, both from the standpoint of safety and ease of doing the work, and when it was seen there was a possibility of using a lighter jackhammer through the use of tungsten-carbide bits and at the same time get at least the same drilling efficiency as with the standard equipment, it was decided to test tungsten-carbide bits. The claims for long life of the bits and footage drilled before resharpening gave hopes of eliminating much of the delay time in changing bits which is unavoidable with the use of steel bits. and thus gain in actual drilling time.

Jan 1, 1949

By J. F. Myers, F. M. Lewis

C. G. McLACHLAN*-I have read this paper with considerable interest and wish to congratulate the authors on the care with which they carried out their experiments and for the detailed sizing data they have presented. 011 the other hand I do not feel that these data establish their contention that "with other factors the same, the work accomplished in a fine crushing rod mill is directly proportional to the rotating speed." My reason for making this statement is that their conclusion is based on the percentage of minus 65 mesh material produced at each of the speeds at which their tests were run. The rod mill is, however, not a fine grinding machine and therefore figures based on minus 65 mesh production are figures outside the range at which it operates to best advantage. Further, if rod mill performance is to be judged on the production of such material it should have been established that a rod mill will produce it as effectively as a ball mill. To check this last point I have gone over some of the rod and ball mill grind-ing figures for our Waite-Atnulet operation and find that the ball mill at that property produces more minus 65 mesh material per horsepower than the rod mill. Moreover, this comparison is even more favorable to the ball mill if it is limited to minus 100 mesh production. It therefore seems to me that the most satisfactory basis on which to try to com-pare the performance of the rod mill in the present case is by taking a weighted average of all the new surface produced per horsepower. W. H. Coghill3 has published data which can be applied to the sizing figures presented by the authors, and if this is done the units of new surface per horsepower produced in the Tennessee tests are as follows: Admittedly the increment of increase in new surface per horsepower shown in the foregoing figures is not great, but its trend is nevertheless definitely in favor of slower speed operation, for the conditions under which these particular tests were run. I also feel that some information regarding liner contour should have been given as I think it will be found that a mill which is equipped with liners which lift the rod load can be run at a slower speed than a mill in which the liners are comparatively smooth. J. F. MYERS and F. M. LEWIS (authors' reply)—The position taken by Mr. McLachlan is to be respected even though we are all aware of the faults of surface considerations. As he points out. the increment of increase is very small. It is so small in fact that for all practical purposes it does not conflict with the conclusions of the paper. The authors appreciate Mr. McLachlan's comprehensive study of the data.

Jan 1, 1950

By Elmer W. Pehrson

Minerals have played a prominent role in the affairs of man and nations since time immemorial but with the advent of the industrial revolution, expanding use of the products of the mineral kingdom became synonymous with the material progress of mankind. Individuals and business groups have recognized this fact so have been aggressive in searching for and utilizing mineral resources, with notable success. Indeed, their achievements are primarily responsible for the present Machine Age. On the other hand, until recently the body politic has failed to grasp fully the essentiality of minerals although, at times, access to mineral supplies has been an important factor in the political maneuvers of nations. This chapter is concerned primarily with the broader political and economic relationships of mineral resources to the world economy, and with the internal and external actions of nations in the field of minerals. Many factors that condition the mineral economy of regions and the world as a whole, influence the internal and external affairs of individual nations. The more important of these are: 1. The nature of man's dependence on minerals. 2. The problems resulting from the unique characteristics of mineral occurrence. 3. Geopolitical concepts. 4. Minerals and world power. Actions of individual nations affecting their mineral economy seek two basic objectives: 1. Attainment and maintenance of prosperity. 2. Military security. Other objectives may be cited but on careful analysis they become integral parts or extreme phases of the two points noted above. For example, the twentieth century aggressions of the USSR, Germany, Italy, and Japan might be considered as direct bids for world power but they also can be interpreted as exaggerated or mistaken efforts toward military security and peacetime prosperity. Similarly, trade barriers, nationalization of industries, foreign exchange manipulations, taxation, monopolistic prac-

Jan 1, 1964

By Francis A. Thomson

DO the curricula of our mineral technology schools prepare their graduates to meet properly the full range of their responsibilities in after life? An unequivocal "no" could be returned to this question, because training and experience in professional work are quite as important as adequate college preparation. Furthermore, a had curriculum with a splendid corps of men doing the teaching and a competent body of students doing the learning will produce a better result than an ideal curriculum in the hands of unqualified teachers and poorly prepared students.

Jan 1, 1937

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By C. Feng, W. E. Krul

A study was made of the development of texture and the anisotropy in plastic flow of Ti-8Al-1Mo-1V alloy. Based on Pole figure determinations, the shifting of texture induced by rolling at approximately 400°C was found to be due primarily to slip rotation for the major Portion of the material. Grain boundary shear is believed to be an important factor. The anisotropy of the textured alloy was examined in terms of the variations of yield stress under tension and the ratio of bi -axial strain increments µp, in the temperature range 25" to 290°C. The results were related to Hill&apos;s theory on plastic anisotropy. The Schmid factors of (1100)[1120], (1101)[1120/, and (1101)[1120] slip systems were analyzed and found to be compatible with the observed anisotropy. Cross-slip between these planes was proposed as a possible deformation mode. In a number of published articles, considerable interest has been directed to the possible achievement of texture hardening in hcp metals. Following Backofen, Hosford, and Burke,&apos; this phenomenon was related to the yield criteria of the material and was expressed in terms of the biaxial strain ratio, r = d?w/d?l. The higher the value of r, the greater is the expected potential for texture hardening under certain loading conditions. For a given material, r varies with direction. Such variation can be traced to the anisotropy in plastic flow and can be explained within the framework of the various modes of deformation. Hatch2 found that a high r value coincides with a texture whereby the (0001) pole is closely aligned with the surface normal for sheet materials, Based on the analysis of the slip on the {1010}, {1011}, and (0001) planes, Lee and Backofen3 and Avery, Hosford, and Backofen4 concluded that the resistance to thinning is reduced by the operation of the (0001) <1120> slip system; with this reasoning they were able to explain the low r values (i.e., r « 1) observed in magnesium alloy sheets in the rolling direction and in commercially pure titanium in the transverse direction. The general equation, dealing with plastic flow in a polycrystalline aggregate has been used to correlate the plastic anisotropy and texture. In this expression, T and s are shear and normal stresses, and dri and d? are shear and normal strain increments, respectively. Assuming that five slip systems are operative within each grain and applying the principle of maximum work,5,6 one can determine the m value among the available systems. On this basis, Hosford7 and Chin, Nesbitt, and Williams&apos; were able to correlate m with yield stress under plane-strain compression, and Svensson9 was able to predict the variation of yield stress in textured aluminum. These workers made their analyses from materials in which slip operation is known to be associated with plastic flow. Questions remain regarding the derivation of Hill&apos;s theory on plastic anisotropy,10,11 since it was formulated on von Mises&apos; yield criterion.&apos;&apos; Its ability to deal with other forms of deformation has been in doubt.13 Others have discussed the validity of Hill&apos;s quadratic equation relating strain and yield stress.14&apos;15 For hcp titanium, deformation by various modes of slip and twinning operations has been reported.16-20 If all possible modes of deformation operate and contribute substantially to the plastic flow, it is difficult to imagine how the quadratic expression can suitably describe the anisotropic plastic flow of titanium alloys. Backofen and Hosford15 considered that Hill&apos;s is a macroscopic theory and implied that the major mode of deformation by slip mechanism will adequately describe anisotropy of the material. In the present investigation, slip operation will be shown to play the major role in the development of sheet texture induced by rolling of a commercial titanium alloy. Although twinning and other modes of deformation may also operate, their operation is believed to be secondary. The anisotropic properties of the sheet, which can be expressed in terms of directional variation of r, µp = -d?w/d?l and the yield stress will be shown to be governed primarily by slip operation. MATERIALS AND EXPERIMENTAL TECHNIQUES The titanium alloy chosen for the present investigation had a nominal composition of 8 wt pct Al, 1 wt pct Mo, 1 wt pct V, and 0.1 wt pct interstitial impurities. Sheets varying between 0.1 and 0.15 in. thickness were used. The alloy was received in a condition which was prepared by rolling at 900°C and annealing at 700°C. Subsequently, the sheets were subjected to further reduction in thickness by rolling at 400°C. A total reduction in thickness of 65 to 70 pct was obtained by a series of quick passes in a rolling mill with intermediate reheating. Further reduction in thickness was not possible due to cracking developed at the edges of the sheets. X-ray measurements were conducted in a Siemens and a Norelco unit to determine the texture of the sheets. Reflection techniques were used exclusively with CuK, radiation and a nickel filter. The loss of X-ray intensity due to geometric defocusing was calibrated with a technique described previously." The (0001), (1010), and (1071) pole figures were plotted from 0 to 80 deg, and to present the texture elements quantitatively, inverse pole figures were constructed following the technique described by Jetter, McHargue, and Williams.22 Tensile experiments were carried out at 25", 175",

Jan 1, 1970

By W. A. Anderson

Recrystallization of cold-worked metals has long been known to proceed by a process of nucleation and growth.&apos; When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.1 Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,&apos; since the rate of recrvstallization is thus analyzed into its two component rates3 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;" values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of X and G ovcr appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By R. Kossowsky, W. C. Johnston

CONSIDERABLE experimental data has been published in recent years on a few directionally solidified aluminum base eutectic alloys. The mechanical properties of A1-Al3Ni eutectic have been studied by Lemkey, Hertzberg, and Ford1&apos;,2 and Salkind et a1.3 where the alloy has been demonstrated to behave as a whisker reinforced composite with superior properties over many aluminum alloys. It has also been shown4 that aluminum reinforced with Al3Ni whiskers R. KOSSOWSKY, Member AIME, is Senior Metallurgist, Westing-house Research Laboratories, Pittsburgh, Pa. W. C. JOHNSTON, formerly with Westinghouse Research Laboratories, is Head, Department of Physics, George Mason College, University of Virginia, Fairfax, Va. Manuscript submitted March 28. 1969. IMD__________________ possesses excellent microstructural stability to 508°C. The effect of lamellar structure in A1-CuA12 eutectic was compared3 to the rod-like structure in the A1-Al3Ni eutectic, and was found to be better in low cycle fatigue. This was rationalized3 by postulating that a lamellar reinforcement was more efficient at blocking lateral plastic flow than a rod-like rein-forcement. The purpose of this study is to explore eutectic strengthening in other aluminum base alloys. The Al-Pd system5 forms a eutectic with aluminum and the intermetallic compound A13Pd at 25 wt pct Pd, and has a melting point of 615°C. A13Pd has an orthorhom-bic structure and transforms to hexagonal Pd2A13 at 785°C. Growth characteristics, compression yield strength, creep rupture, and microstructural stability of directionally solidified and as-cast alloys are investigated. Eutectic ingots having a nominal composition of 25 wt pct Pd were prepared by first compacting 1/2 in. diam by a in. high pellets from 99.99+ pct A1 and 99.99 pct Pd powders. The pellets were then levitation cast into 1/4 in. diam by 2 in. long copper molds. Directionally solidified bars were prepared by grinding the cast ingots to 0.195 in. diam, inserting them into alumina

Jan 1, 1970

By M. Cohen, C. Wagner, J. E. Reynolds

If the total volume of a diffusion couple changes during the diffusion, the measurement of distance becomes ambiguous. Use of distance parameters as suggested by Hartley and Crank is discussed. For small concentration differences, the standard form of Fick&apos;s second law is retained with conventional length units and the in- terdiffusion coefficient D. It is shown how D can be calculated from experiments involving large concentration differences and analyzed in terms of distance parameters. &apos;The merits of incremental diffusion couples involving small concentration differences are emphasized. THE conventional form of Fick&apos;s second law for one-dimensional diffusion of component B in a binary solution of A and B is where c, is the concentration of component B; x, the distance; t, the time; and D, the interdiffusion coefficient which may depend on ca. Hartley and Crank&apos; have pointed out that Eq. 1 applies only if the total volume of the diffusion couple does not change during the diffusion process; otherwise, the definition of x becomes ambiguous. No change in total volume takes place if the specific volume of the solution is a linear function of the weight fraction Wb, or if the molar volume is a linear function of the mol fraction N. In some alloys, however, these relationships do not hold, and then it is necessary to introduce a modified measure of distance, 4 in order to retain the general form of Eq. 1. The application of Hartley and Crank&apos;s suggestions to diffusion in alloys has been discussed by Wagner.&apos; Relation Between Measure of Distance and Units of Concentration The definition of [ depends on the choice of units for the concentration c,, as follows: 1—If the concentration ca is measured as the weight fraction W, (or weight percent), [ = 5, has to be defined so that equal increments of contain equal increments of mass m of the solution, e.g., dm = pSdx = Sdw [2] where p is the local density of the solution, and S is the cross-sectional area in sq cm which is taken to be constant in this problem of one-dimensional diffusion." * da Silva and Mehla have demonstrated the constancy of the cross-sectional area in the usual type of diffusion couple. However, experiments involving diffusion into thin wires4, 5 may exhibit changes in cross-sectional area, and therefore are excluded from the present treatment. Thus and the unit of is gram per sq cm instead of cm. 2—If the concentration c, is the mol fraction N, must be defined so that equal increments of contain equal numbers of mols of solution, e.g., dn= (S/V)dx= Sd [41 where V is the local molar volume of the solution. Thus dt, = dx/V [51 and the unit of is mols per sq cm. 3—If, as may be advisable in the case of interstitial solutions, the concentration C is measured in terms of the molar ratio of components B and A (c,, = Y, = nH/nA, where n and nl are numbers of mols of B and A), = Y has to be defined so that equal increments of contain equal numbers of mols of A, e.g., dnA= (NAS/V)dx = Sdf [6]

Jan 1, 1954

By D. R. Hay, E. Scala

STUDIES of structure-sensitive properties, especially mechanical behavior, have shown that grain and subgrain structure play an important role. The mechanical properties of tungsten, in particular, are sensitive to the nature of the intergranular structure. Substructure and dislocation networks in single-crystal and polycrystalline tungsten have been studied by Nakayama et al.&apos; Various orders of substructure were observed ranging from a microscopic first order (grain diameter: 2 to 8 mm) to a microscopic second order (grain diameter: 50 to 300 p), and, within the latter, dislocation networks forming an even smaller order of substructure. In their single crystals, grown by arc fusion, the degree of misorientation in each order was small: 16&apos;3OU, -11, and -10" for the first-, second-, and third-order substructure, respectively. To study the properties of polycrystalline tungsten, powder metallurgy tungsten is generally used. However, in a mechanical property investigation, the zone-melted or arc-fusion crystals are more desirable than the powder metallurgy product due to their higher purity and absence of porosity and other defects inherent in consolidation by powder metallurgy. Grain boundaries can also be produced in melted stock by working and recrystallizing. However, material with subgrain mis orientations of the order of several degrees (high-angle substructure) has not been reported previously and is the subject of this communication. Crystals were grown by electron-beam, floating-zone melting. The starting material, Sylvania Pure-tung welding rod, was given one zone pass at a traversal rate of -2 mm per min. Through control of the zone temperature, it was possible to influence the degree of crystal perfection. By maintaining the zone at a high degree of superheat, high-perfection crystals could be grown. However, at temperatures only slightly above the melting point, the zone-melted crystals contained a high-angle substructure. A sensitive control of the zone temperature was not possible due to the difficulty of estimating the temperature of the zone and of providing a constant supply of power to the sample. Therefore, an empirical method, using the shape of the molten zone as a criterion, was adopted as an indication of temperature. At high degrees of superheat, the surface tension of the molten zone decreases and a neck forms at the top of the zone, whereas at low zone temperatures the diameter of the zone remains reasonably uniform. Although it was not possible to obtain a continuous variation of misfit angle, the conditions could be directed toward the growth of either high- or low-angle substructure by maintaining only a slight neck in the zone (sufficient to establish that it was molten) or a well-necked zone, respectively. Mass spectrographic analyses of both types of material revealed no significant differences in the concentrations of their impurities. The degree of misorientation at high angles was obtained by measuring the angular spread of spots corresponding to a single reflection on a Laue back-reflection photograph. Fig. 1 shows a typical Laue back-reflection photograph of a crystal with a 3-deg spread. By measuring the angular deviation of the spots corresponding to a single reflection from the mean center of the spots around which constant angular deviation contours were drawn, an average angular spread of misfit could be calculated. The angular average was weighted by the number of spots observed in each angular interval. At angles greater than 5 to 6 deg the spots from different reflections begin to overlap, and cannot be associated with a particular reflection. Laue back-reflection photographs taken at different locations on samples .with approximately 3-deg spreads showed only a small difference in angular misorientation, less than 8&apos; of arc, within individual specimens. The microstructure was examined using Berg-Barrett X-ray extinction contrast microscopy. Berg-Barrett photographs taken directly on the as-grown surface, Fig. 2, show an essentially equiaxed subgrain structure of -0.1 mm in average grain diameter in both high- and low-angle crystals. Fig. 2(a) is a photograph of a sample with a low misfit angle and Fig.

Jan 1, 1968

By S. H. Chauvenet

Jan 1, 1882

By M. A. Grossmann

THE hardenability of most steels can be predicted within 10 to 15 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a &apos;&apos;pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain sue may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter"; namely, the diameter of bar, in inches, that will just harden all the way through (absence of un- hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test. The data bring out certain features rather clearly. For example: I. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals," are known; thus an "incidental" chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybde- num when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful as wouldappear to be common experience; observe that an increase from no manganese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added " 20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the first small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using 1.0 per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost lo per cent in hardenability (in these units); this, however, does not apply to certain steels of high hardenability. It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome- molybdenum and chrome-vanadium steels, undissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum possible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the absence of Cr, and V up to 0.04 per cent), the charts provide reasonable approximations. The precise figures on the charts are suggested as tentative, subject to some modification as more data accumulate, but the fundamental concept appears to be supported by tests made on a wide variety of steels, a few of the correlations being shown in Fig. I.

Jan 1, 1942