Search Documents

By A. Gatti, R. L. Fullman

A very fine dispersion of aluminum oxide is produced by internal oxidation of solid-solution alloy of 0.14 pet A1 in Ag. The particle size of the aluminum oxide is approximntely 50 to 100A in radius. The yield strength of the alloy is increased markedly by internal oxidation. A further increase in strength is produced by cold working the internally oxidized alloy. Recrystallization is retarded by the finely dispessed aluminum oxide particles, so that the strength increase resulting from cold work is retained on annealing at temperatures 14 to about 700°C. MANY workers'-3 in the past have studied various aspects of the internal oxidation of aluminum-silver alloys. This paper is an extension of these studies with emphasis placed on the effect of time and temperature of annealing on the strength of these alloys after oxidation and subsequent cold working. Two general conditions are necessary to internally oxidize an alloy. First, oxygen must diffuse through the base material more rapidly than does the addition; otherwise oxidation will take place as a surface layer. Secondly, the affinity of oxygen for the addition must be greater than for the base material. After internal oxidation of certain alloys takes place, a marked increase in hardness accompanied by higher yield stress and improved creep properties is noted, presumably as a result of the highly dispersed oxide within the base material. Meijering and Druyvesteyn1 also noted that the internally oxidized portion of a partly oxidized alloy failed to recrys-tallize under annealing conditions that led to coinplete recrystallization of the unoxidized part. EXPERIMENTAL-METHODS AND PROCEDURES Few alloys can be made to contain a second phase that is extremely stable at high temperatures. Silver plus aluminum in solid solution was chosen for these internal oxidation studies because of the high rate of oxygen diffusion through silver and the very stable nature of aluminum oxide. Two alloys were vacuum cast. The nominal compositions were: Alloy A—1 pct Al, balance Ag; Alloy B—0.1 pct Al, balance Ag. Chemical analysis, which does not distinguish between aluminum and aluminum oxide, showed the conlposition to be: Alloy A—1.6 pct Al, and Alloy B—0.14 pct Al. The ingots were machined for surface cleaning, swaged and drawn to 0.020-in. diam wire. A sample 20 ft long of the 0.020-in. dianl wire of each composition was annealed 24 hr at 800°C in pure dry hydrogen. Each wire was then cut into two equal pieces. Photomicrographs of the 0.14 pct A1 alloy are shown in Fig. 1, the annealed 0.020-in. wire at the left and the oxidized wire to the right. The oxidation treatment for the first set of data was 1000 hr at 800°C in air. After this treatment the 1 pct A1 proved to be brittle. It is assumed that high alunlinum oxide concentration at the grain boundaries was responsible. The 0.14 pct Al wire remained ductile and all further data were derived using this alloy. One-half of this wire, about 5 ft, plus 5 ft of as-homogenized wire, was then drawn cold to 0.005 in. diam. All tensile tests were conducted with an Instron Engineering Corp. tensile-testing machine, Model TT-B. Unless otherwise indicated, the tests were made at room temperature with a strain rate of 0.1 per min. All metallographic samples were etched with an aqueous solution of 2 pct each of CrO3 and H2SO4 . EXPERIMENTAL RESULTS AND DISCUSSION PARTICLE SIZE DETERMINATION A study was made of the particle size of the aluminum oxide produced in the samples of Ag + 0.14 pct Al, oxidized 1000 hr at 800°C. A cross section of the as-oxidized wire was mounted in bakelite, polished, and etched with an aqueous solution of 2 pct each of CrO3 and H2SO4. The specimen was then thoroughly cleaned by stripping successive coatings made by applying 10 pct nitrocellulose in amyl acetate. The final replica of the cross section was made by applying 2 pct nitrocellulose in amyl acetate. The replica was stripped, transferred to a copper screen, shadow cast with chromium at 10 deg and photographs taken using a Phillips Metallix electron microscope at an accelerating potential of 100 kv. A photograph of an etched sample of the as-oxidized material is shown in Fig. 2. We believe the pits in the photograph are places were A12O3 inclusions were sitting in the matrix. By inspection, it appears that the volume fraction ob-

Jan 1, 1960

By L. A. Geoffrion, R. H. Perkins, J. C. Biery

Densities of cerium metal and several lour-melting binary cerium alloys were measured over the range 25° to 800°C. A rolumeter, using NaK as working fluid, was used to obtain the data. The cerium, Ce-Co, Ce-Ni, and Ce-Cu alloys all exhibited an increase in density on melting, while a Ce-Mn alloy expanded on melting. FOR the proper design of a nuclear reactor, the change in density of the fuel with temperature must be known. This is especially important in a system utilizing molten fuel, such as LAMPRE (Los Alamos Molten Plutonium Reactor Experiment), since a relatively large change in density usually occurs during the solid-liquid transition. The fuel for LAMPRE is a Pu-2.5 wt pct Fe alloy with a melting temperature of 410°C. However, limitations in reactor design with this fuel have led to consideration of other plutonium-containing alloys for use in future generations of this type of reactor. Several ternary alloys containing plutonium and cerium as two components have satisfactorily low melting points. The system that at the present time appears to be most acceptable is Pu-Ce-Co; it exhibits little change in melting temperature with wide variation in plutonium concentration. Other alloys that have received some consideration contain nickel, copper, and manganese as the third constituent. The proposed fuel alloys are difficult to handle experimentally in the 25" to 800°C temperature range since they oxidize readily, react with many solvents, and contain a poisonous fissionable material. In addition, in this temperature range the alloys pass through the solid-liquid transition. Several techniques are available for measuring the densities and volume coefficients of expansion of solids or liquids. However, the only apparatus that appears suitable for measuring expansion coefficients over this temperature range and through the phase transition is a volumeter. In a volumeter, the indicating medium must be essentially inert to and insoluble in the material being studied. It must also possess a low vapor pressure over the operating temperature range, and its coefficient of expansion must be accurately known. One material that is satisfactory in nearly all of these respects is the alloy Na-78 wt pct K, which melts at -10°C and has a vapor pressure of 860 mm Hg at 800°C. This relatively high vapor pressure at 800°C requires an overpressure of an inert gas to prevent boiling. While a volumeter is capable of determining accurately the volume coefficients of expansion of materials, it cannot be used for absolute density measurements. Therefore, a density determination at a known temperature must be coupled with the volumeter measurements to give all the desired data. The weight-loss technique using immersion in bromobenzene at room temperature proved to be satisfactory. The preliminary work that was done on this experimental program involved developing and calibrating the equipment, and measuring the densities and volume coefficients of expansion of cerium and some low-melting binary cerium alloys. The complications that are caused with the introduction of plutonium into the system were avoided until the equipment was proved to be satisfactory and until experience was gained in its operation. It is this first phase of the experimental work that is described in this report. DESCRIPTION OF EQUIPMENT AND OPERATING PROCEDURE The NaK volumeter is shown schematically in Fig. 1. Basically, the equipment consists of two weld-sealed stainless-steel containers of nearly identical volume. One container holds a tantalum crucible and the specimen being measured; the other contains a tantalum crucible and a tantalum specimen used as a control reference material. To avoid temperature gradients, the bombs are located in a copper block inside the furnace. Stainless-steel capillaries of equal length and volume connect each stainless-steel container to a glass viewing capillary. The stainless-steel containers, stainless-steel capillaries, and a portion of the glass capillaries are filled with NaK (22 wt pct Na-78 wt pct K). The NaK/gas interface in the glass capillary is viewed with a cathetometer which is accurate to *0.5 mm. The cathetometer readings are used to calculate the volume changes of the samples during a run. This volumeter is basically the same as that described by F. Knight in Plutonium 1960. 2 However, changes in equipment design and operating procedure were made to eliminate some major operating difficulties. These changes are summarized below. 1) In filling the manometer with NaK, gas was frequently entrained in the system. Evacuation of the system before filling failed to eliminate the en-

Jan 1, 1965

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By U. K. Custred, E. W. Long, V. R. Degner

In 1973, the United States production of marketable phosphate rock set a record in excess of 42 million tons. This production rate is expected to continue to increase, due to the growing international requirement for fertilizer, at a rate exceeding 5% per year well into 1977. One approach towards increasing plant production capacity to meet the growing demand is through large-capacity flotation cells, provided they achieve metallurgical performance comparable to existing smaller cells. A 9-month evaluation test program recently completed at the Haynsworth mine at Bradley, Fla., demonstrated the feasibility of achieving economically acceptable concentrate grade and recovery levels using large, high-capacity flotation cells. The composition of the feed to the Haynsworth beneficiation plant is a typical Florida pebble phosphate matrix composed of phosphorite pebbles ranging in size from approximately 1-1/2 in. down to 150 mesh and intimately associated with a mixture of clay and sand (essentially silica). The feed contains approximately 22 to 28% phosphate reporting as tricalcium phosphate, Ca3 (PO,) 2, or "bone phosphate of lime" (BPL). The flotation section utilizes the double-float procedure typical of Florida plants. The phosphate is first floated away from the silica in the rougher circuit, using crude fatty acid, ammonia, and fuel oil or kerosene. Rougher conditioning is accomplished at 60 to 70% pulp solids with sufficient ammonia added to raise the pH to 9 to 9.5. Following coarse and fine rougher flotation, the concentrate (overflow) streams are joined and conditioned (sulfuric acid cleaned and washed) prior to entering the cleaner circuit where an amine float (cationic reagent and kerosene added in the feed box; pH 7.3 to 7.8) is employed to float the silica. The feed to the coarse rougher circuit averages 29% +35 mesh while the fine rougher feed averages 10%+35 mesh. Primary attention was directed toward the large rougher cell performance (recovery and grade) on coarse feed during the Haynsworth evaluation program. Flotation Cell Test Program A row of three No. 120 size (300 cu ft) WEMCO flotation cells was installed in parallel with an existing air-cell row. The total installed volume of the large cell circuit was 900 cu ft and required a floor space of 306 sq ft. This compared to the air-cell total volume of 200 cu ft and 152 sq ft floor space. (Both floor areas include feed and tails hoppers but exclude walkways.) Fig. 1 is a schematic cross section of the large flotation cell showing the relative location of key mechanism elements. In operation, the rotor generates a fluid vortex extending up along the walls of the standpipe and creating a sufficient vacuum within its core to ingest air into the standpipe/rotor cavity through the air inlet duct. The ingested air mixes with the pulp, which has been recirculated through the false bottom and draft tube, in the rotor. Further mixing occurs as the air and pulp move radially outward from the rotor, finally passing through the disperser into the flotation cell. Flotation is accomplished outside the disperser, where phosphorite laden air bubbles rise and the remaining pulp recirculates down along the cell wall to the false bottom and draft tube. Large-flotation-cell performance is influenced by the ability of the mechanism to (1) circulate, or suspend, the solids in the pulp; (2) ingest air into the rotor cavity; and (3) mix the air and pulp effectively. The proper balance between pulp circulation and air ingestion is a key consideration in achieving good recovery in a course feed application. Large-flotation-cell pulp circulation and air transfer characteristics are significantly influenced by rotor speed and rotor submergence; therefore, these two operational parameters can be used to "optimize" a particular mill application. Fig. 2 maps the hydraulic performance of the WEMCO No. 120 size flotation cell. This map can be used to relate the cell operational parameters which influence metallurgical performance. At a given rotor speed, power intensity (i.e., pulp circulation) is seen to increase, and airflow decrease, as rotor submergence is increased. The inverse relation between power and airflow is due to the two-phase air-liquid mixture density reduction accompanying the increased airflow rate. For any fixed rotor submergence, the power intensity (i.e., fluid circulation) and airflow both increase as rotor speed is increased. The selection of these two mutually related operating conditions (i.e., rotor speed and submergence) was a key consideration in the Haynsworth evaluation program.

Jan 1, 1976

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By M. G. Benz

The superconducting performmce of diffusion-processed Nb3Sn is influenced by its micro structure. High isotropic transverse current density may be achieved in this material by a process which forms a precipitate of ZrO, within the Nb3Sn. FOR an ideal type-I1 superconductor, little or no transport current can be carried in the mixed state; i.e., little or no transport current can be carried above the lower critical field H,,, where the field penetrates abruptly in the form of current vortices or fluxoids, even though full transition to the normal state does not occur until the upper critical field H,,.&apos; Fortunately, nonideal type-I1 superconductors can be readily obtained and these carry large transport currents up to the upper critical field H. Both theoretical and experimental investigations have attributed this current-carrying capability for nonideal type-I1 superconductors to pinning of the fluxoid lattice by heterogeneities in the microstructure of the superconducting material. These heterogeneities may take the form of dislocations or dislocation clusters,2"5 grain boundaries: structural imperfections introduced by phase transformations; radiation damage,8"10 or precipitates.11"15 Nb3Sn formed by diffusion processing is a type-I1 superconductor. Heterogeneities are needed for high superconducting critical currents above H,,. This paper will cover: a) what the microstructure of diffusion-processed NbSn looks like; b) what changes in the microstructure take place when the system is doped with precipitates, and c) how these changes in microstructure influence the superconducting critical currents. EXPERIMENTAL Preparation of Samples. Diffusion processing was used to form the Nb3Sn. The procedure used was as follows: a) coat the surface of a niobium tape with tin; b) heat-treat this tape at a temperature above 930°C to form a layer of Nb3Sn at the Sn-Nb interface. Such a layer of NbsSn is shown in Fig. 1 The thickness of the NbsSn layer formed was controlled by the time and temperature of the heat treatment. The same general procedure was used for preparation of both undoped samples and samples doped with a precipitate. An additional step was included in the preparation of the doped samples which consisted of internal oxidation of zirconium to form ZrOn. The details of the doping process will be reported in a later paper. Sample Testing. The Nb3Sn tape samples were soldered to a copper or brass shunt. Current and voltage leads were then attached to the sample in the usual four-probe resistance measurement configuration. The sample was cooled to 42°K. In some cases it was cooled in the presence of a high magnetic field and in other cases with the field turned off. The results were the same for both cases. The samples were oriented in a configuration with field transverse to current but could be rotated such that the angle between the field vector and the wide side of the tape sample could be changed. Measurements up to 100 kG were done in a superconducting solenoid and measurements above 100 kG in a water-cooled copper magnet at the MIT National Magnet Laboratory. Once the test field was reached, the current in the sample was increased until voltage was detected across the sample. The critical current was taken as the current at which voltage was first detected in excess of background noise. In most cases this was 1 to 2 x 10~6 v for a— in.-wide sample carrying several hundred amperes with a in. separation between voltage leads and with a 10 "-ohm shunt resistance. RESULTS AND DISCUSSION Microstructure. Examination of the microstructure of the undoped Nb3Sn shows rather large-diameter (1 to 2 columnar grains growing outward from the niobium surface toward the tin surface. As the layer is made thicker by longer diffusion times, these grains grow longer. Few new grains are started. Transmission electron microscopy shows little or no second-phase material within the bulk of the Nb3Sn layer. The microstructure of a diffusion-processed NbsSn layer changes quite drastically when the system is doped so as to form a precipitate within the NbsSn layer. Instead of large-diameter columnar grains of NbaSn forming, smaller-diameter (0.5 to 1 ) equiaxed grains of Nb3Sn decorated with the precipitate form. Fig. 2 shows a transmission electron micrograph of a Nb3Sn layer doped with zirconium oxide. This layer has been etched so that one may look between the grains

Jan 1, 1969

By D. A. Augenstein, L. V. Amundson

Operators of coal preparation plants use equipment such as large-capacity dump trucks and bulldozers to haul, spread, and compact refuse material to conform to federal and state regulations governing the disposal of solid waste. For example, federal regulations require that refuse be spread and compacted in layers not more than 0.6 m (2 ft) thick. If the refuse layers or piles have poor load-bearing characteristics, movement of equipment over them becomes extremely difficult. The increasing cost and limited space for the construction of settling ponds extensively used for fine refuse disposal are leading to the growing practice of dewatering the fine refuse by means of vacuum disk filters and combining the resulting filter cake with coarse refuse for waste bank disposal. However, this filter cake usually contains more than 25% moisture. Therefore, when it is combined with coarse refuse, the moisture level of the total refuse may become high enough to impair the load-bearing strength of the refuse. Precisely this problem and the attendant difficulties of moving heavy equipment arose when vacuum disk filters were installed at a preparation plant in West Virginia. Combining the moist filter cake with the coarse refuse generally results in a 12% moisture level for the total refuse at this plant. At this moisture level, the refuse can still be handled with some dif¬ficulty by the equipment. However, the problem has frequently been compounded after rains. The experimental program described in this paper tested the following methods of improving the load-bearing properties of coal refuse: moisture reduction, addition of crushed coarse refuse, addition of fly ash, addition of lime, and addition of a mixture of lime and fly ash. In terms of a balance between economic and technical considerations, the most effective method was demonstrated by laboratory and plant tests to be a 2% to 5% addition of lime. Test Program During formulation of a test program aimed at improving coal refuse stability, a number of treatment techniques were selected for evaluation of their effect on refuse load-bearing characteristics. The reduction of refuse moisture was the first technique considered, since moisture content plays a key role in the bearing strength of a bulk solid. The reasoning was that a very small reduction in refuse moisture, provided it could be accomplished with minimal effort and cost, would be sufficient for eliminating refuse disposal problems most of the time. At the same time, it was recognized that periods of rainy weather would offset moisture-reduction measures. Other techniques selected for evaluation because of their potential for improving refuse-bearing strength at reasonable cost were: addition of crushed coarse refuse, the addition of fly ash, and the addition of lime. A simple one-dimensional laboratory compaction test was designed for evaluating the effect of each of these techniques on refuse-bearing strength. Those techniques that gave best results in the laboratory would then be tested in the preparation plant in West Virginia. Laboratory Tests The laboratory test for evaluating each of the techniques involved the application of weight to a load module placed on a refuse sample in a container. The distance the load module sank with an increasing amount of applied weight was measured, and the relationship between module displacement and loading was obtained. The refuse container was large enough to minimize the influence of wall effects, and to decrease the effect of the container bottom, a test was terminated when the load module sank to about three fourths the depth of the container. Initially, an attempt was made to conduct compaction experiments with samples of total plant refuse. However, the presence of + 0.13 m (+ 5 in.) material in the refuse interfered with the mechanics of the test, and the large amount of material required for a representative sample made testing extremely tedious and time-consuming. To avoid this problem and because it was believed that only the fine components of the refuse were the major cause of the stability problem, tests were conducted with 13 mm X 0 (1/2 in. X 0) material from the total plant refuse. The equipment consisted of a 0.46 m (18 in.) cubic container, a loading module with 62 cm2 loading area, weights totaling 450 kg, and a portable concrete mixer for combining water and additives with the refuse. Refuse samples of about 110 kg dry weight were used for each test. Experimental compaction test data were evaluated by plotting the linear displacement of the load module vs. loading. During compaction tests, the vertical displacement of the load module was measured at each loading value. The plot of

Jan 1, 1980

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By D. Atkinson, C. Bodsworth, I. M. Davidson

A geometric model of interstitial solid solutions, which has been used previously as a basis for the prediction of carbon activities in Fe-C austenite, is shown to serve also for the calculation of nitrogen activities in Fe-N austenite. The model has been developed to enable predictions to be made of the activities of an interstitial element in the presence of two host atom species. The activities calculated via the model are shown to be in satisfactory agreement with the measured values in the austenite phase for carbon in Fe-C-Co, Fe-C-Cr, Fe-C-Ni, Fe-C-~n, Fe-C-Si, and Fe-C-V alloys and for nitrogen in Fe-N-Ni alloys. The effect of the second substitu-tional solute on the logarithm of the activity of the interstitial element is expressed as the product of a constant mad the atomic concentration of that solute. The constants so derived we related to the thermo-dynamic interaction coefficients which describe the effect on the activity coefficient of carbon of an added solute element. In recent years the thermodynamic activities of carbon and nitrogen in the single-phase austenite field have been determined for iron binary alloys and for several iron-base ternary alloys. In order to extend the use of these measurements, it is desirable to be able to predict with reasonable accuracy the activities of the interstitials at compositions and temperatures other than those which have been measured experimentally. In all the systems studied to date, the interstitial elements do not conform to ideal behavior. Hence, the available data cannot be extrapolated or interpolated using the simple thermodynamic concepts of solutions. Several models have, therefore, been formulated for the purpose of predicting the activity of an interstitial element in the presence of one species of host atom. These models can be divided into the geometric1"5 and energetic6-&apos; types. The former group is based on the assumption that at low concentrations the activity of the interstitial species is determined by a composition-dependent configurational entropy term and an excess free-energy term which is temperature-dependent but independent of composition. The purpose of this paper is to show that the treatment, based on a geometric model, can be extended to enable predictions to be made of interstitial activities in the presence of two substitutional host atom species. THE CONFIGURATIONAL ENTROPY OF MIXING ICaufman5 has shown that the configurational entropy, S,, for a binary solution comprising of a host atom species, A, and an interstitial species, I, can be expressed as: where NI is the atom fraction of the interstitial species, R is the gas constant, and (2 - 1) is the number of interstitial sites excluded from occupancy by the strain field around each added interstitial atom. The number of interstitial sites per host atom, p, is unityg for the fcc austenite solutions considered here. The configurational entropy of mixing for a ternary solution comprising two substitutional atom species, A and B, and one interstitial species, I, can be derived similarly. Let the number of atoms per mole of each of these species in the solution be represented by «a, ng, and nI. From geometric considerations, it is improbable that the addition of a few atom percent of a second host atom species will change the type of sites (i.e., octahedral) in which the interstitial atom can be accommodated in the austenite lattice. At higher concentrations (determined largely by the relative atomic radii of the atomic species present and any tendency to nonrandom occupancy of the host lattice sites) other types of interstitial sites may become energetically favorable. Restricting consideration to compositions below this limit, for 1 = 1 the number of suitable interstitial sites is given by (n + nB). However, if each interstitial atom excludes from occupancy (Z - 1) additional sites, the total number of sites available for occupation is reduced to (n + ng)/Z. The number of vacant interstitial sites is given by: The total number of recognizable permutations of the atoms must include the recognizable, different configurations of the A and B atoms on the host lattice. Assuming that these arrangements are purely random, and are not affected by the presence of the interstitial species, the total number of recognizable permutations in the ternary alloy is given by: The configurational entropy is obtained by expanding, using Stirling&apos;s approximation, and collecting like items, as:

Jan 1, 1969

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz&apos; to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""&apos;"&apos;"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15&apos;F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By J. W. Spretnak, G. W. Powell, J. H. Bucher

Tlze room-temperature tensile fracture oj smooth, round specitnens of three ultrnhigh- strength steels tempered to a wide range of strength levels was studied by means by light and electron-microscopic examination of the fracture surfaces. The fracture of AISI 4340 and 300 M at all the strength levels studied, and H-11, except after tempering at 1200° and 1300°F, occurs in three stages. The initiation of fracture is internal (except in some lightly tcmpeved specimers in which fracture is initiated at surface flaws), and is nucleated largely by separation at metal-second phase intevjaces. TIze voids grow and, coalesce to form a crack. When the crack has reached a sufficienl size, rapid propngutio~z ensues. Failure in this stage of fracture usually occurs by dimpled rupture of inicroshear stefis. In the case of H-11 tempered in the 1125° to 1300°F range, fracture in the shear steps is predominantly by concentrated deformation without void formation. The termination of fracture is usually occomplished by the formation of a shear lib in which fracture occurs by shear dimpled rupture. In the case of H-11 tempered at 1200° and 1300°F, no shear lip was obserued, and the radial elelments extend to the surface—a true termination slage does not exist. ThE tensile fracture of several metals and alloys has been investigated.2-4 In the case of polycrystal-line materials, cup-cone fracture usually results. The mechanism of cup-cone fracture may be summarized as follows.5 Cavities are formed in the necked region of the specimen. They usually are initiated by inclusions or second-phase particles. The cavities extend outwards by means of internal necking, and a crack lying about perpendicular to the length of the specimen is formed in the necked region. Subsequent crack growth occurs by the spread of bands of concentrated plastic deformation inclined at an angle of 30 to 40 deg to the tensile axis. Cavities are formed in the bands of concentrated deformation. The deformation bands zigzag across the bar with the net result that mac-roscopically the crack extends about perpendicular to the specimen axis. The final separation, or cone formation, appears to occur by continued crack propagation along one of the deformation bands out to the surface of the specimen. The micromechanics of the tensile fracture of ultrahigh-strength steels have not been thoroughly investigated. Larson and carr6,7 studied the tensile-fracture surfaces of AISI 4340 with a low-power microscope and reported that three stages of fracture could be observed in general. A centrally located region characterized by circumferential ridges, an annular region characterized by radial surface striations, and a peripheral shear lip were found. It was first pointed out by 1rwin8 that the central region is very probably one of fracture initiation and slow growth, and that the annular, radially striated region is one of rapid crack growth. Presumably the crack grows slowly, assuming roughly a lenticular shape, until it is large enough for the initiation of rapid propagation. In this investigation, it was attempted to determine the fine-scale aspects of the room-temperature tensile fracture of some ultrahigh-strength steels, and to relate the variation in fracture mode with microstructure. The steels studied were AISI 4340, 300M, and H-11 tempered to a wide range of strength levels. I) EXPERIMENTAL PROCEDURE The compositions of the steels studied are given in Table I. The steel was received in the form of hot-rolled bar stock 5/8 to 1 in. in diameter from which oversized specimens were machined and heat-treated. The heat treatments employed are given in Table 11. Subsequent to heat treatment, the specimens were ground to the final dimensions and stress-relieved by heating for 1 hr at 350°F (with the exception of the as-quenched steel). Standard smooth round specimens of 0.252-in. diameter and 1-in. gage length were tested in a Tinius Olsen Universal Testing Machine using a cross-head speed of 0.025 in. per min. The relatively coarse aspects of the fracture topography were determined by light-microscopic examination of sections through the fracture surface of nickel-plated specimens. A direct carbon-replication technique9 was used in the electron-microscopic study of the fracture surfaces. The replicas were examined in the electron microscope, and stereo pairs of electron micrographs were taken. The stereo pairs were then examined using a Wild ST4 Mirror Stereoscope. Carbide and inclusion particles extracted in the replicas were analyzed by selected-area electron diffraction. II) EXPERIMENTAL RESULTS The mechanical testing data are summarized in Table 111. The values reported are the average of

Jan 1, 1965

By W. F. Chiao, R. B. Gordon

Tile sharp-yield point found in magnesium crystals in the solulion-treated and aged condition is studied by dislocation internal-friction experiments. The results show that the sharp yield is not file to the sudden release of pinned dislocations hut is movc likely due to the rapid multiplication of an initially small number of dislocations. Recovery or the dislocation internal friction after deformation is also studied. This yecovery results from the re-pinning of dislocations by a solute, presumably nitrogen, which moves with a relatively small activation energy. SHARP-yield points, when they occur, are a striking feature of the stress-strain curve generated during a tensile test. Although commonly associated with steel, sharp yielding has been found in a variety of metallic and nonmetallic crystalline materials. In particular, sharp-yield points have been found in zinc"&apos; and cadmium3 containing nitrogen. With this background, Geiselman and Guy4 investigated the tensile properties of magnesium single crystals containing nitrogen to see if sharp yielding also occurs in this system. They found that sharp yields did indeed occur in solution-treated and aged specimens tested at elevated temperature but were not able to give conclusive proof that the sharp yield was caused by nitrogen, a yield drop being observed even in their purest crystals. Sharp-yield points have also been found in various polycrystalline magnesium alloys.7&apos;8 In the study of the sharp-yield phenomenon it is desired to observe the behavior of dislocations in the earliest stages of the deformation process. Internal-friction experiments are useful for this purpose because dislocation damping is sensitive to the mobility of free-dislocation segments. At low strain amplitudes the damping, A, due to the the forced vibration of dislocation segments of average length L is ? =KAL4 [1] where A is the dislocation density and K, if the applied frequency is well below the resonant frequency of the dislocation segments? is a constant for the sample under observation.5 Dislocation damping, because of the fourth-power dependence on L, is particularly sensitive to the creation of free-dislocation segments during deformation. Since sharp yielding is associated with the sudden release of pinned-dislocation segments, marked changes in the dislocation damping are expected at the yield point.6 The use of the dislocation-damping observations to help elucidate the incompletely understood mechanism of yielding in magnesium is the primary objective of the experiments reported here. PROCEDURE Many investigations have shown that very marked and rapid changes occur in the dislocation damping of of a deformed material as soon as the straining is stopped.5 It was quite essential, then, for the purpose of this investigation, to make the damping measurements during the deformation of the samples. This can only be accomplished through the use of the ultrasonic-pulse method. In this method traveling sound-wave pulses are used and, in contrast to resonating-bar methods, only the sample ends are set in vibration. Thus, the sample can be gripped along its sides in the tensile-test machine without disturbing the damping measurements. In the pulse method, the decrease in the amplitude of a sound pulse is measured as it travels back and forth through the sample. If A is the amplitude after traversing a distance x and A. is the initial amplitude, A=Aoe-ax [2] and a is called the attenuation. It is commonly measured either in units of cm-I or as db per µ sec. The observed attenuation in a metal sample is due to a number of causes. These include scattering by grain boundaries and impurity particles, thermo-elastic damping, diffraction effects, stress-induced ordering of solute atoms, and dislocation damping. The total observed attenuation in a given sample usually cannot be resolved into these various components, but changes in a due solely to changes in dislocation damping can be accurately determined, provided the experiment is arranged so that all other sources of damping are held constant. It is desired to reduce the extraneous sources of attenuation to a minimum and for this reason the experiments are done on single crystals of high purity. Magnesium crystals offer the further advantage that, when properly oriented, only a single set of slip planes is active during deformation. Crystal Preparation. The method of sample preparation is similar to that of Geiselman and Guy.4 The starting material was high-purity, sublimed magnesium rod supplied by the Dow Chemical Co. Melting under Dow 310 flux was used to reduce the nitrogen content of the starting material: the fluxing was done under an argon atmosphere and the

Jan 1, 1965

By C. Gatlin, F. Armstrong, K. E. Gray

This paper presents some preliminary results of two-dimensional cutting tests of dry limestone samples at utmospheric pressure. Cutting tips having rake angles of + 30°, + 15", 0°, - 15" and - 30" were used to make cuts on Leuders limestone samples at six depths of cut ranging from .005 to ,060 in. at cutting speeds of 15, 50, 109 and 150 ft/min. The vertical and horizontal force components on the cutting tips were recorded with an oscilloscope equipped with a polaroid camera. Motion pictures of the cutting process at camera speeds of 5,000 to 8,000 frames/sec were taken at strategic points in the variable ranges. The movies provide considerable insight into the brittle failure mechanism in rocks. It appears that chip-generating cracks usually have an initial orientation which is related to the resultant of the externally applied forces. The latter part of the crack curves upward toward the free surface being cut, this part being governed by some type of cantilever bending or prying. The linear and angular motion of the loosened chips also indicate the tensile nature of brittle failure. Analyses of the forces on the cutting tips indicate that: (I) relatively small increases in vertical loading result in large cut-depth increases for sharp tips (rake angles 2 0"); (2) tool forces increase at an increasing rate as the rake angle decreases, particularly for rake angles < 0"; and (3), for the range of this study, rate of loading had little effect on the maximum forces. Both the movies and visual inspection of the cuttings indicated that the volume of rock removed by chipping was much larger than that by any grinding mechanism, even for tips having negative rake angles. Cutting size increases with increased cut depth and rake angles, and decreases slightly at high cutting speeds, the depth of cut having by far the most influence. The amount of contact between the rock and the cutting tip was always less than the depth of cut and rarely exceeded 0.010 in. even for cuts of 0.060 in. INTRODUCTION The planing (or slicing) of various materials with a fixed blade has long been practiced by workers in many industries. For example, the farmer&apos;s plow, the carpenter&apos;s plane and the housewife&apos;s paring knife all employ this basic action. The casual observer might suspect that something so common must be quite simple; however, as in all problems involving the failure of materials, such is not the case. Industries concerned with the machining of metals have long studied these problems, and their literature on the subject is voluminous. Despite these efforts, basic knowledge is not very advanced, as may be noted from recent and comprehensive analyses of their literature.12 Metals are more subject to analysis by classical theories of elasticity and/or plasticity than are rocks, since their elastic constants and strengths are reasonably well established in many cases. In spite of this relative "simplicity", Hill9 refaces his discussion with an admission that the mathematical solution to the machining problem is not known. Photoelastic studies of both machining and milling have been performed and are discussed thoroughly by Coker and Filon.4 Rotary drilling of rocks with fixed blade or drag bits has long been practiced by the mining and petroleum industries, and considerable study has been given to defining their cutting action in terms of the pertinent variables. Essentially all the published mechanistic research on drag-bit drilling has been performed by mining engineers and has been concerned only with rocks in the brittle state. Fairhurst5-7 has worked extensively in this area and employed photographic techniques quite similar to those reported here, except at much lower speeds. His studies showed the periodic or cyclical nature of the brittle failure mechanism, in which instantaneous loads on the bit varied from some maximum value to near zero. Goodrichs has presented further data on the subject as well as a qualitative description of the process. Again the postulated mechanism is cyclical, with alternate chipping and grinding periods. The ploughing of coal is a practiced method and has been studied in some detail by English mining engineers."" Their findings have considerable general application to drag-bit drilling. Evans," in particular, has extended Merchant&apos;s metal-cutting theory" to brittle materials with some success, although certain aspects of his theory are open to question. Fish13 has recently summarized nearly all the published works concern-

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By K. E. J. Rapperport, C. S. Hartley

The only slip system observed in zirconium crystals deformed at 77", 575", and 1075OK was (1010) [1210] with a critical resolved shear stress in tension of 1.0 kg per sq mm at 77°K; 0.2 kg per sq mm at 575 °K; and 0.02 kg per sq mm at 1075 OK. The active twin planes were {1012}, (1121}, (11221, and (11233) with varying temperature dependence. A detailed analysis for the slip direction using Laue spot asterism is appended. NeARLY all metals of the hexagonal close-packed structure exhibit basal slip, i. e.,(0002)<1120>- type slip. This is true of magnesium,&apos; zinc,&apos; cadmium,3 beryllium,4 titanium,= yttrium,6 and rhenium.Many of these such as titanium 5&apos;8-&apos;0beryllium,4&apos;" magnesium, and zinc13&apos;14 display other slip modes even at room temperature, and nearly all have been reported to slip on other systems under particular loading or temperature conditions of testing. As is shown in this paper, basal slip was not found at any of four test temperatures from 77" to 1075°K in hexagonal close-packed zirconium under the simple loading conditions of tension and compression, even though in one case the resolved shear stress on the inactive (0002) <llgO> system was twenty-five times higher than the critical resolved shear stress on the active (1010) [1210] system. This result is consistent with prior studies on the active deformation processes in zirconium deformed at room temperature. &apos;&apos;-I7 SPECIMEN PREPARATION A) Material—The zirconium used in this work was of two types: 1) as-deposited reactor grade crystal-bar, and 2) arc-melted and forged reactor grade crystal-bar. Typical chemical and spectrographic analyses of these materials as received, and after hydrogen removal and crystal growth are given in Ref. 17. Crystals of type 1) above have the letter prefix (A) and those of type 2) have the prefix (B) throughout this paper. B) Crystal Growth— he zirconium was machined into rectangular parallelepipeds about 0.2-in. scl in cross section and 2 in. iong. These were hand polished through 4/0 abrasive paper, electropolished, given a hydrogen removal anneal, and subjected to long-time anneals at 840 °C in vacuo to produce usable crystals.&apos;7 A second technique used to obtain large crystals was to cycle the samples two or three times between 1200" and 840°C, allowing them to remain at the higher temperature for about 4 hr and at the lower temperature for 5 days.17 These techniques yielded some grains which occupied the entire cross section of the bar and were as long as 3/4 in. C) Orientation Determination—After the growth of large crystals by thermal cycling, the samples were repolished with extreme care through 4/0 abrasive paper and electropolished. Metallographic examination after polishing showed the surfaces to be free of visible deformation traces. Standard Laue back-reflection X-ray techniques were used to find the crystallographic orientations of selected large grains with respect to a specimen face and edge. Fig. 1 shows the stereographic projections of the stress axes for the crystals used. The sharpness of the spots on the Laue photographs indicated that the crystals were of good quality. EXPERIMENTAL METHODS Nine crystals were deformed in tension at 77"K, nine in tension and five in compression at 300°K in previous tests,17 fifteen in tension at 575"K, and eleven in tension at 1075°K. All specimens were stressed by load increments. After a predetermined load was applied, the specimen was removed from the loading appratus and metallographically examined for deformation traces. An attempt was made to initially stress each bar so that some crystals slipped a small amount and others not at all. This was done to bracket the critical resolved shear stress. One bar of special orientation (B-11) was repolished and annealed at 1075°K for 1 hr after lower temperature deformation, before final deformation at 1075°K. In the other bars the loading by increments, followed by metallographic examination, was continued until the surface distortion would interfere with analysis, or until fracture. One example of a crystal pulled to fracture is shown in Fig. 2. This photograph shows a crystal (B-14C) which was pulled at 1075°K and failed by slip on two (10i0) planes. The approximate orientation of this crystal is illustrated in the figure. Specimens were deformed at 77°K in liquid nitrogen on a tensile machine using an insulated bucket with an internal hook to accept a clamped specimen.

Jan 1, 1961

By S. C. Sun, John A. L. Campbell

The surface properties exhibited by bituminous coal and bituminous coal lithotypes were ascertained by using streaming potential techniques. The electro kinetic prop-erties wereascertainederties of bituminous coal were found to be similar to those of anthracite. The principle electrokinetic properties of the coal and lithotypes, zero-points-of-charge (ZPC), and potential determining ions, were established. The effects of indifferent electrolytes, hydronium and hydroxyl ion sources, and polyvalent ions (cationic and anionic) were also evaluated. Location of the ZPC&apos;s with respect to pH is discussed in terms of chemical and mineralogical composition of the respective surfaces. To account for the observed electrokinetic phenomena, a generalized surface model and adsorption mechanism are proposed. Surface-dependent processes, such as froth flotation and flocculation, are important or potentially important techniques for combating some of the current major problems in coal preparation. In order to correctly apply or improve a surface-dependent process, it is of paramount importance to understand the interfacial phenomenon, especially the double layer properties, exhibited by the solid. The specific objective of this research was to determine the properties of the bituminous coal/liquid interface by an electrokinetic method, streaming potential, and to relate the findings, wherever possible, to the existing unit operations of froth flotation and floccula-tion tion. The electrokinetic properties of both the whole coal and its lithotypes were investigated. As part of the total investigation, the role played in the double layer by the reagents commonly employed in the surface dependent process was also established.&apos; These data will be presented at a later date. Experimental Procedures The coal samples used in this research and their designations are listed in Table 1. The classical description of humic coal lithotypes as developed by Stopes" was used for the delineation of the lithotype samples. The samples were taken from the working face of a producing deep mine of the Pittsburgh seam in the area of Ellsworth, Pa. To avoid oxidation, only freshly exposed areas were sampled. The normal precautions against contamination were also exercised. Two types of samples were taken, specimens rich in a particular lithotype and a representative channel sample. The latter sample was prepared for analyses by grinding it to —35 mesh. It was screened repeatedly during the grinding to provide the largest amount of 35 x 48-mesh (standard Tyler sieves) material possible. The screened fraction was passed over a magnet and then washed several times with distilled water and finally with conductivity water. The resulting sample now termed "whole coal" was stored under conductivity water in a glass bottle. Pure lithotypes were obtained from the lithotype concentrates by hand picking, and were processed in the same manner as the representative sample. Maceral analyses, employing standard petrographic procedures," were performed on the lithotype samples to determine the purity of the samples. The results are presented in Table 2. Reflectance measurements of the vitrinites and fusinites are also reported in this table. Proximate and ultimate analyses of the samples are given in Tables 3 and 4. The electrokinetic properties of the coal samples were determined by streaming potential methods.&apos;-&apos; All of the chemicals used in the investigation were reagent grade (Baker analyzed). The conductivity water was prepared by doubly distilling the water in a pyrex Yoe-type still and passing the distillate through a mixed bed ion exchange column. Results In general, the electrokinetic properties of the investigated bituminous coal were found to be similar to the results of a previous study of anthracite by Camp-bell bell5 and are in accord with the suppositions of Brown." The zeta potentials of the coal and all the lithotypes were found to be negative in conductivity water. Jowett? in a study of slime coatings on coal also found bituminous coal to exhibit a negative surface. Fig. 1 shows that the negative charges, at neutral pH&apos;s, for both fusain and the gangue are very small, almost zero, while at the same pH, vitrain has the largest negative charge, almost 30 mv. Durain has a negative charge of 17.5 mv. The determination of the affect of pH on the charge of the coal surfaces revealed that hydronium and hydroxyl ions apparently behave as potential determining ions; however, they do not appear to be potential determining for the gangue. These results are illustrated in Fig. 1. As the pH of the solution was decreased, hydronium ions were adsorbed, causing the surface of the coal to reverse polarity and become

Jan 1, 1971

By H. C. Chao, L. H. Van Vlack

Small MnS inclusions with known crystallographic orientations were placed inside powder compacts of low-carbon steel. After the metal was axially campressed with negligible end friction, the deformstions for the metal and the inclusions were compared. The MnS inclusions deformed more when the [100] direction was aligned with the compression axis than when the [111] direction was parallel to this axis. The deformations of the inclusions in the two principal radial directions were equal for each of the above orientations. Inclusions with [110] compression alignments did not deform with radial symmetry. The relative deformation of the inclusion and metal was closely dependent upon the relatiue hardness of the two phases. The relative deformation of the two phases was not sensitive to the rate of deformation. RECENT studies by the authors1.&apos; suggested that the plastic deformation of MnS in steel would probably be highly sensitive to the orientation of the inclusions and to the temperature of the metal. This paper reports an investigation of these factors upon MnS behavior within steel. Manganese sulfide (MnS) possesses an NaCl-type structure and typically has extensive (l10) {110} slip as a separate (noninclusion) crystal.&apos; A secondary slip system, ( l 10) { l l l}, has also been observed where the major slip system is restricted. In general, MnS inclusions must be rated as a highly deformable second phase.3 The amount of sulfide deformation varies, however, with several composition and processing factors. Some of these have been only partially assigned. For example, it is known that minor amounts (<0.01 pct) of silicon within free-machining steels will increase the amount of MnS deformation,4 but the mechanism of the added deformation can only be surmised at the present. Manganese sulfide and steel have sufficiently comparable deformation characteristics so that slip which is started in steel may be continued through the sulfide inclusions and back into the steel if the crystal orientations are favorable.5 A more detailed discussion of previous work on the plastic deformation of NaC1-type crystals and on the plastic deformation of inclusions within a metal is given in Chao&apos;s work.6 EXPERIMENTAL PROCEDURE The manganese sulfide which was used in this study was prepared by previously described methods.&apos; Single crystals of MnS, both as cleavage cubes and as spheres, were oriented within steel powder compacts so that the desired crystal directions were parallel to the direction of axial compression. A four-stage hydrostatic compaction procedure was used and involved the following steps. In the first stage part of the powder was placed in a metal die 1 in. in diameter with a thick (1 in. OD, 5/8 in. ID) rubber liner which had one end plugged. The steel powder was hand-rammed, making it as dense as possible before placing a carefully sized MnS crystal (either as a sphere or as a cube) near the center. The crystal was oriented with the chosen direction vertical; viz., [001], [011], or [111], with the aid of a X10 microscope. A pair of tungsten wire threads 0.020 in. in diameter was inserted along the side of this (&apos;core compact" to locate the desired plane after the compression tests. After the crystal was positioned in the center of the die, more powder was added and carefully rammed by hand. The die was then capped with a rubber plug of the same hardness and thickness as that of the liner. The whole assembly as shown in Fig. 1 was compacted by a ram load of 54,000 lb (about 70,000 psi). In the second stage a smaller, 3/4-in, rubber-lined die was used to give a stress of approximately 120,000 psi. The above process was repeated with the initial compact serving as a core for a larger compact. The final product after sintering was a cylinder 1 cm long and 1 cm in diameter, having a density of 7.54 g per cu cm. This was close to the theoretical density since the metal contained a non-metallic phase. There was no evidence of MnS deformation during the hydrostatic compaction or subsequent sintering. Elevated-temperature hardness data were obtained by procedures previously described.2 Compression tests for inclusion deformation utilized the cylinders which were described above. The critical problem in these tests was the lubri-

Jan 1, 1965

By C. S. Matthews, H. C. Lefkovits

Drilling progress is often delayed by sticking of the drill string. The development of preventive and remedial methods has been hampered by incomplete understanding of the sticking mechanism. A recent lahorntory investigation hns indicated that one type of sticking may be attributed to the difference in pressure between the borehole and formation. This paper shows, by means of soil mechanics, that the primary cause for differential pressure sticking is cessation of pipe movement, whereas diflerential pressre and stanrtding time determine the severity of the sticking. The analysis stresses the importance of using low-weight muds with low solids content and low water loss to alleviate diflerential pressure sticking and describes why packed hole drilling, long strings of drill collars, and a large deviation from the vertical are conducive to sticking. Finally, preventrve and remedial methods ore evaluated, and a theory is presented on the release of stuck pipe by spotting oil. INTRODUCTION Since drilling with long strings of oversize drill collars has become standard practice in many areas, the incidence and severity of the stuck pipe problem has increased. It has been noticed that in the majority of these cases the sticking could not possibly be attributed to key seating or caving of shales. It appeared that, due to the differential pressure between the mud column and the formation fluid, the collars were pressed into the wall and so became "wall stuck". Points to note about differential pressure sticking are: (1) sticking is restricted to the drill collars, (2) the collars become stuck opposite a permeable formation, (3) the sticking occurs after an interruption of pipe movement, (4) circulation, if interrupted, can be restarted after the sticking is noticed, and (5) no large amounts of cuttings are circulated out after restarting circulation. Helmick and Longleyl investigated pipe sticking by differential pressure in the laboratory and found an empirical relationship between the differential pressure, the sticking time and the required pull-out force. In this paper an explanation of the mechanism is given based on Terzaghi&apos;s theory of clay consolidation. A qualitative description is given in the following paragraphs while the derivation of fonnulas is given in Appendices. This paper is a first attempt to explain pressure differential sticking and many points will require additional theoretical and practical investigation before the problem can be fully understood. PRESSURE DIFFERENTIAL STICKING AS A CONSOLIDATION PROBLEM In any borehole, where the mud pressure is higher than that exerted by the formation fluids, a mud cake is formed opposite the permeable sections of the hole and a continuous flow of filtrate takes place from the mud, through the cake and into the formation. This radial flow pattern requires a certain distribution of the hydraulic and the effective (grain-to-grain) stresses inside the mud cake. Any quantitative or qualitative change in the external pressure conditions will produce a change in the flow pattern and, consequently, also in the internal stress distribution inside the cake. In view of the low permeability and the high compressibility of a clay mud cake, the adjustment of the internal stress distribution is slow and is accompanied by a change in volume. Time dependent stresses are thus created which gradually diminish as the new state of equilibrium between internal and external pressures is approached. Some 30 years ago, Terzaghi developed his "Theory of Consolidation" to account for the time-dependent stresses and settling of clay formations under the influence of external loads. He derived a differential equation by which the time-dependent hydraulic stress and the consolidation can be computed for any point inside the layer during the consolidation process. His theory is based on the assumption that the change in stress is solely due to a change in water content and it may only be applied to one-dimensional consolidation phenomena. Other investiga-tors5,10 have expanded his theory to include processes of more than one dimension. The difference between the external pressures on the mud cake before and after sticking is a qualitative one (isolation of part of the cake by the static contact with the drill collars after pipe movement has been stopped)&apos;, and the time-dependent stresses thus created may be investigated by means of Terzaghi&apos;s theory. By this analysis the changes in the nature of the contact surface between the drill collars and the mud cake during the sticking can be explained; and the friction force between the two may be computed as a function of the sticking time, the borehole dimensions and the mud cake characteristics.

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the &apos;&apos;Annales des Mines" (French), page 19. R. F. Schurtz (Author&apos;s Reply) Mr. Duval&apos;s position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah&apos; in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.&apos; studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.&apos; studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h&apos;hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969