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By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By Francis M. Walters

IN spite of the war and the preoccupation of many physical metallurgists with work on secret or confidential problems, definite progress was made during 1944 in our understanding of the behavior of steel and of the effect of alloying elements. During the first two years of the war there was much concern over the possible unavailability of certain alloying elements; this period saw the development of the N.E. (National Emergency) steels. However, the measures taken eased the alloy situation and currently, highly practical problems under study are the graphitization of low-carbon steel and weld-cracking, while investigations of more theoretical interest have concerned hardenability, isothermal reactions, the effect of hydrogen and the interpretation of the notched-bar impact test.

Jan 1, 1945

By C. W. Robinson

Transportation is the minerals business. Once upon a time the geologist, the engineer and later the metallurgist reigned supreme, but the leading role in mineral development today is the economist-especially the transportation economist. Obviously this trend is more important for large volume, low value mine-to-market movements of such commodities as iron ore, phosphate, potash, coal and petroleum. But, transportation is of sufficient importance to all mining activities to be included in forward planning. Civilization has been influenced by transportation developments to an extent little understood or appreciated. Although industrialists are capable of intelligent historical analysis of this phenomenon, too frequently they have failed to project, or anticipate those changes in transportation techniques which will influence the pattern of industrial growth.

Jan 1, 1971

By C. H. Herty

AN earlier paper on absorption of sulfur by the slag in the basic open-hearth furnace included a brief discussion of the absorption of sulfur during the melting period. The data available at that time showed that the amount of sulfur absorbed by the melting scrap was proportional to the sulfur content of the furnace gases, and the following statement was made: "The conclusion may be drawn from these results that if a gas entirely free from sulfur were used during the melting, any iron in direct contact with the gases would be completely, or nearly completely, desulfurized before it reached the bath proper." The experimental work discussed herein deals with absorption of sulfur by the melting scrap when fuels with both high and low-sulfur content were used. Before taking up the experimental work let us consider the process as a whole as to the "flow" of sulfur. The input of sulfur occurs in: 1, the hot metal charged; 2, the scrap; 3, the stone or lime charged; 4, the ores charged; and 5, the gas. Sulfur goes out of the furnace in the steel, the slag and the gas. The distribution of sulfur in the furnace depends on the sulfur concentration in each of these materials and on the equilibrium conditions between them.

Jan 1, 1926

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By E. Amott

A test is described in which the wellubility of porous rock is measured as a function of the displacement properties of the rock-water-oil system. Four displacemet operations are carried out: (I) sponlaneous displaceti?ent of water by oil, (2) forced displacement of water by oil oil in the same system using a centrifuging procetllrre, (3) spontaneous displacement of oil by water. and (4) forced displacment of oil by water. Ratios of the spontaneous displacement volumes to the total displucenlent volumes are used as wettability indicates. Cores having clean mineral surfaces (strongly preferentially water-wet) show displacement-by-waler ratios approaching 1.00 and displacement-by-oil ratios of zero. Cores which ([re. strongly preferentinlly oil-wet give the reverse resu1ts. Neutral wellability cores show zero values for both ratios Fresh cores from different oil reservoirs have shown wettabiltties in tlris te.st covering rrlti~ost 111e conlplrtt, range of thr: te.st. Notvever, nlo.s/ of tlle fresh California cores tested were slightly prcfere111icrlly wclter-\vet. The chrrnge.~ in coro u ('liabilities, as indicated hy this te.st, r~.sril/ing from various CO~P hanrlling procedures tt,ere oh.served. In sonie ca.sc,s /Ire ~,cttahilitio.c. of fresh cores were changell by drxi:~g or 11y e.x/rclct ing with iolcreiii~ or. dioxunc~; in o/h~r cases they were 1101 changed. Co~ltrrc/ of cort,.s ~.ith filtrc~t~c. from water-base rlrilling rilrrrls crlrc.sed littlc change in we/ /ahility ivhile contnct with filtrates frorii oil-hus~ ri1rlcl.s tlecrrascrl the prefcrerlcc, of the, cores for )I.NI Usitig thi,s test to ri.crl~lute n~r~ttubili~y, N .vt~ldy was iilarle of /lie correlmtio~i of wettability with wa/erfloocl nil recovery for orttcrop Ohio sand.stone and for Al~ln-tlunl. Resul/.v indicate thml no single correlatioti between these factors applies to different porous rock syste~n. It is thought that diflerences in pore gen~netry resrrlt in diflrrerrce.~ in this correlurio~z. INTRODUCTTON Most investigators who have reported on the wettahility of porous rock have described such rock as prcferentially water-wet or preferentially oil-wet. In some cases a third classification, neutral wettability. has been used. The efficiency of water floods in each of these wettability groups has been described in numerous publications. Several methods for characterizing porous rock wet tability more precisely have been reported,' " but it appears that because of one weakness or another. none of these has been generally accepted. Early in our studies in this field, it was found that the displacement efficiency of oil by water in a particular porous rock having a strong preference for water was quite different from that in a similar rock having only a moderate preference for water. Thus, there appeared to be a need for a practical, reasonably precise wet tability test. one which could classify porous rocks into 10 to 20 different groups rather than the two or three broad groups listed above. The test developed to meet this need is described in this paper. Also, changes in wettability, as indicated hy this test, resulting from various core handling procedures are discussed. Finally, data showing the corrclation of wettability with waterflood oil recovery for two different types of cores are presented and discussed. Some confusion has resulted from the failure of certain writers to define clearly some of the wettability terms they have used. Accordingly, the following commcnts concerning definitions are offered. The wc t ta-hility of a solid surface is the relative preference of that surface to be covered by one of the fluids under consideration. It is felt that this is the generally accepted definition. The fluids being considered must bc specified (or understood) before the term wettability has any significance. In the work reported here these fluids are water (3 per cent brine) and oil (kerosene). The term preferential wettability is sometimes used, but we think that the word preferential is redundant here and should not be used. Tn line with the definitions of Jennings', a preferentially oil-wet solid surface is regarded as a surface which will show an oil advancing contact angle less than 90" (measured through the oil) in the water-oil-solid system. Oil will spontaneously displace water, if both are at the same pressure, from such a surface. A preferentially water-wet surface is analogous. This is consistent with the wettability definition above. As Jennings has said, frequently the term oil-wet is used to mean the same thing as preferentially oil-wet. However, oil-wet also has been used occasionally referring to an oil-covered surface when the availability of water was limited. To avoid confusion from this source, we do not use the terms oil-wet and water-wet. DESCRIPTION OF WETTABTLITY TEST The following points were considered desirable in a wettability test for our purpose. 1. The test should be a displacement test resembling

By Klaus-Peter M. Hanke

INTRODUCTION In early 1979 Jim Walter Resources, Inc. (JWR) of Brookwood, Alabama approached TMCI Construction, Inc (TMCI) to make a proposal on a program that involved the sinking of up to 10 ventilation shafts of approximately 6.7 m (22 ft) diameter and ranging in depth from 500 to 700 m (1650 to 2300 ft) for the JWR coal mines in Alabama. At this time TMCI was already constructing the first spiral underground bunker (capacity 2000 tons) in North America for the JWR organization at their No. 4 mine in Alabama. The TMCI proposal was based on the use of the mos modern large diameter shaft boring machine rather than sinking the shafts using the conventional drill blast-muck technique. The proposal was made based o: the experiences by the parent company, Thyssen Schachtbau, which has been using this type of machin in Germany for shaft boring since 1971. As a result of the TMCI proposal JWR issued a purchase order to TMCI for the construction of four 6.7 m (22 ft) diameter, concrete lined, unfurnished ventilation shafts ranging in depth from 500 to 700 (1650 to 2300 ft). An order was thus placed with WIRTH Machinen- and Bohrgeraete Fabrik GmbH, in Germany for the manufacture of a model 650/850 E/Sch "Schachtbohrmaschine" (Vertical Shaft Borer = V-mole which arrived on site in Alabama in early 1981. The first V-mole GSB 450/500 was introduced in Germany in 1971 and was capable of enlarging in one step a pre-drilled 1.2 m (4 ft) pilot hole to 4.5 - 5.0 m (14.7 - 16.4 ft). This machine has sunk 9 staple shafts and deepened one surface shaft for a total of 2360 m (7740 ft) of shafts. On the last shaft boring operation in 1978 the machine was converted as an experiment to drill without a pilot hol using a hydraulic pumping system to remove the cutting debris. A second generation machine, the SB VI 500/650, was introduced in 1977 for enlarging the pilot hole to a range of 5.0 - 6.5 m (16.4 - 21.3 ft) diameter. This machine is still in operation and has already drilled well over 2000 m (6500 ft) of shaft. The third generation of V-mole, the SB VII 650/85( for diameters from 6.5 to 8.5 m (21.3 to 27.9 ft) was: commissioned in May 1980 and has been used for two surface shaft deepenings totalling 606 m (1990 ft) with another scheduled for 1982. The main advantages favouring the use of such V-moles were identified as: 1) A reduction in manpower to the crew required in a conventional shaft sinking operation. 2) A considerable reduction in time to complete a shaft compared to conventional techniques. 3) The use of the V-mole eliminates many of the hazards encountered in conventional sinking. Based on the successful performance of the first three V-moles in Germany, Thyssen Schachtbau decided to employ this principle abroad. In 1980 a second machine of the third generation was built and is now operated by TMCI Construction, Inc. in Alabama. The first shaft was completed at the end of 1981 and this paper describes the method of operation including some unique aspects not attempted on prior V-mole operations and some of the statistics arising out of the experiences during the first shaft boring operation. THE NO. 7 MINE FAN SHAFT SITE Jim Walter Resources, Inc. was formed in 1970 to exploit the coal field in Alabama on the southern tip of the Appalachian coal field. The coal reserves amount to around 650 million tons of mainly good quality coking coal of which about 350 million tons are to be extracted over the next 30 years. Shaft sinking and preparatory work began in 1972, and at present 6 mines are producing around 5.4 million t.p.a. Annual production is to expand to 10 million t.p.a. as soon as possible, and the ventilation shafts to be sunk by TMCI play a vital role towards attaining this goal. The first shaft site is located at the No.7 mine, near Brookwood, Alabama. The actual location of the shaft relative to the production shafts is shown on the mine plan (Fig. 1), which also shows the room-and-pillar extraction system used at present. The mine plan further shows the conveyor route used for the muck removal. The geological survey showed that the strata consisted of horizontal layers of mainly sandstone, sandy shale and shale interspersed with several coal seams. The seam being extracted at the No. 7 mine is a combined seam made up of the Blue Creek and Mary Lee seams at a depth of 513 m (1682 ft) and having an average seam thickness of about 2 m (6 ft). At the beginning of September 1980 the surface site preparation and pre-grouting work was completed by JWR, and TMCI was able to commence with Stage I of the shaft sinking program - the drilling of the pilot hole.

Jan 1, 1982

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,' has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-' in fcc metals, vary from 1 to 10~6 sq cm sec-'. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"' content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10' cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6' 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown's formula.'' Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown's estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid binary and ternary Fe-Ni-Co alloys has been measured by the Sieverts' method between 1550°and 1700°C. Solubility data and standard free energzes and enthalpies of solution for nitrogen in the alloys are presented. Interaction parameters are discussed and presented for binary and ternary alloys. MOST of the studies of nitrogen solubility in liquid metals have been directed toward the dilute alloys of iron. Several of these investigations have included measurements of the nitrogen solubility in Fe-Ni al10s'- and in Fe-Co alloys.435 There has been some work, however, that has extended across the e-i-" and F-CO" binaries. This investigation was undertaken to determine the nitrogen solubility in both binary and ternary alloys of the Fe-Ni-Co system. It was also hoped that the differences between earlier studies might be resolved. EXPERIMENTAL METHOD This investigation was made using a Sieverts' apparatus described previously." The nickel (99.85 pct) and cobalt (99.9 pct) were obtained from Sherritt-Gordon Mines, Ltd., and the iron (99.95 pct) was Fer-rovac-E obtained from Crucible Steel Co. Recrystal-lized alumina crucibles were used throughout the entire investigation with no evidence of crucible-melt reaction. Melt temperatures were measured with an optical pyrometer and the temperature scale calibrated against the melting points of the three pure metals. The emissivity of the melt was assumed to be a linear function of composition for all alloys, as has been shown for Fe-Ni alloys.lZ The emissivity of the pure metals at 1600°C were taken as 0.43 for iron, 0.44 for cobalt, and 0.45 for nickel. Using these emissivities, the trans mis sivity of the system was found to be 0.51 i 0.01. The Sieverts' method was used for this study and followed the procedures outlined previously.l' The individual metals were weighed to give about 100 g of alloy. The alloys were melted in the crucible under a partial pressure of argon. The system was evacuated, and the "hot volume" was measured with argon. To avoid the errors caused by vaporization, the melt was held under vacuum only long enough to ensure that all of the gas in the system had been removed. The influence of any small amount of vaporization on the "hot volume" was shown to be negligible by measuring the "hot volume" after a run. This measurement agreed with that made at the start of the run within the implicit error, 0.2 cc, caused by the limitations in accurately reading the buret. The solubility-pressure relationship was measured in the pure metals and in several alloy compositions throughout the ternary system. These measurements were made by admitting measured amounts of nitrogen to the system, and then determining the equilibrium nitrogen pressure above the melt. This method has the distinct advantage of higher accuracy, particularly at lower pressures, than measurements made by withdrawing gas from the system to reduce the pressure after determining the solubility at 1 atm nitrogen pressure. This latter method has a practical lower limit of about 0.4 atm where an increased error is encountered because the buret must be emptied to permit further measurements at lower pressures. By determining the relation between apparent solubility and pressure, it was possible to make a good estimate of the initial nitrogen content of the metal from the intercept of the solubility curve extrapolated to zero pressure.11 DISCUSSION The solubility data corrected to 1 atm nitrogen pressure are summarized in Table I. The reported solubility has been corrected for the initial nitrogen content of the alloys. The initial nitrogen contents fell between 0.0002 and 0.0010 wt pct, and were lower in the iron and nickel than in the cobalt. Sieverts' law was obeyed in all alloys at pressures up to 1 atm. Examples of this behavior are shown in Fig. 1. The reaction for solution of nitrogen is Taking the standard state as 1 wt pct N in the alloy and the reference state as nitrogen at infinite dilution in the alloy, and noting the adherence to Sieverts' law, K becomes the solubility of nitrogen in the alloy at 1 atm pressure. Thus the solubility data of Table I were used directly to calculate the standard free energy for the solution reaction. These results are also presented in Table I. The enthalpy of solution is also summarized in Table I as calculated from a form of the van't Hoff relation: Iron-Nickel System. The data for the solubility of nitrogen in liquid Fe-Ni binary alloys is presented in Fig. 2 along the with data of aito, Schenck et al.,' and Humbert and 1liott.l' The data for studies of nitrogen solubility in Fe-Ni alloys containing less than 20 pc t i'- are not presented in Fig. 2, although they are in good agreement with the present work. The results of this study are in good agreement with Schenck

Jan 1, 1967

By E. Miller, K. Komarek, W. Johnson

The activity of aluminum in solid Cr-A1 alloys has been measured by an isopiestic technique between Cr-A1890' and 1126" and 13 and 80 at. pct Al. The integral free energy of mixing has a minimum value of —5600 cal per g-atom at 59 at. pct Al. The maximum solid solubility of aluminum in chromium was determined to be 43 at. pct Al, and the composition limits of the compounds CrA14, Cr4A19, and Cr5Al, at 1000"~ were found to be 79 to 80, 66 to 70, and 59 to 63 at. pct Al, respectively. The thermodynamic properties of the Cr-A1 system have been investigated as part of a thermodynamic study of aluminum-transition metal systems.172 Little information is available on the equilibrium properties of the Cr-A1 system. The heats of formation of solid Cr-A1 alloys have been determined by Kubaschewski and Haymer at 600" and low-temperature specific heat data have also been obtained.~ More extensive work has been performed on the phase diagram, and a compilation has been provided by Hansen and Anderko,~ their phase diagram at elevated temperatures being essentially based on the work of Bradley and LU.~ The high-temperature portion of the phase diagram shows an intermediate phase CrA14 decomposing peritectically at 1018°C and existing at 82 at. pct A1 at 1000°C. They also identified the compounds with solubility limits of 72 to 75 at. pct A1 at 1000°C, and Cr5A1,, existing at 61 at. pct A1 at 1000°C. The maximum solid solubility of aluminum in chromium at 1000°C was found to be 46 at. pct Al. These elevated-temperature data were obtained by examination of quenched samples and were considered as less precise than the lower-temperature data. Koester, Wachtel, and Grube7 have revised the phase diagram as a result of their magnetic susceptibility and X-ray study. The results of this work differ appreciably from those of Bradley and Lu at temperatures above 800°C. The CrA1, compound is given as existing between 79 and 81 at. pct A1 at 1000°C, and they do not indicate the presence of a CrA13 phase reported by Bradley and Lu. They also report the compound Cr4Alg as having solubility limits of 66 to 70 at. pct A1 at 1000°C, while Bradley and Lu show this compound stable only up to 870°C. Koester et al. state that the high-temperature modification of the compound Cr5A18 is stable down to 1125"C, and not 980°C as stated by Bradley and Lu, and that the low-temperature modification of Cr5Al, has a range of homogeneity of 58 to 63 at. pct A1 at 1000°C. They also report that the maximum solid solubility of aluminum in chromium is 43 at. pct A1 at 1000°C. APPARATUS AND EXPERIMENTAL PROCEDURE An isopiestic method was employed which has been successfully applied to the determination of aluminum activities in solid ~e-All and Ni-Al alloys. Alloy specimens were held at different positions in a temperature gradient and were equilibrated with aluminum vapor from an aluminum reservoir kept at the temperature minimum of an impressed thermal gradient in a closed alumina system. Diffusion of aluminum into the specimens occurred until equilibrium was reached, at which the partial pressure of aluminum in each of the specimens was given by the vapor pressure of the pure aluminum reservoir. The activity of aluminum referred to liquid aluminum as the standard state in a given equilibrated sample at temperature T could therefore be expressed by: vapor pressure of pure aluminum at _ the temperature of the reservoir Vapor pressure of pure liquid aluminum, at specimen temperature T Since both the temperature of the aluminum reservoir and the specimen temperatures were determined experimentally, and the vapor pressure of pure aluminum is known as a function of temperature,' the activity of aluminum in a given aluminum alloy of known composition could be calculated. Initial runs were made with samples consisting of pure chromium chips placed in alumina crucibles. These runs exhibited large inconsistencies, indicating that equilibrium was not attained. High aluminum content Cr-A1 alloy powders were therefore substituted for the pure chromium specimens. The starting composition of the alloys was adjusted through experimentation until the concentration change necessary to attain equilibrium was small. In this manner, consistent results were obtained in reasonable times. SPECIMEN PREPARATION Alloy specimens were prepared from chromium of 99.997 pct minimum metallic purity: with 0.028 to 0.038 pct H, 0.0002 pct N, and 0.27 to 0.46 pct 0 (Aviquipo, Inc.). The aluminum had a purity of 99.99+ pct and the following impurities: 0.003 pct Cu; 0.002 pct S; 0.002 pct Fe; 0.001 pct Pb; 0.001 pct Ga (Aluminum Corp. of America). Alloy powders were prepared from weighed mixtures of chromium and aluminum by double-arc melt-

Jan 1, 1969

By M. S. Azun

I do not at all agree with the basic points of the author's conclusion. The use of lognormal or normal model to respond to the attribute distribution function should be carefully questioned. If fitting a distribution function of regionalized variables is the main purpose, one may employ one of certain well-known families of distributions, such as Tukey's lambda functions. For instance, the distribution function of gold assay values studied by Krige (Krige, 1978) may fit the lognormal model well, but one should not exclude that the basic idea of using the distribution function of observed data is to have insight of the physical mechanism that gives rise to the regionalized variables. In Applied Geostatistics, there are many examples considering only lognormal or normal model for the distribution function of geostatistical data even if the observed distribution function has more than one mode. Of course, using lognormal or normal model always brings easy computation for the statistical properties of attribute under investigation. Still, I object to adopting any of those models without having any "statistical inference." As seen from the author's paper, lognormal and normal model produce the same average grade (0.746% copper) and almost the same sample variance. Therefore, which model explains the probabilistic behavior of ore deposit is always an important question that should be replied by the geostatistician using not the common sense but the statistical and probabilistic methods. For kriging procedures, such as linear kriging, one should describe either second order stationary properties or bivariate properties of regionalized variables. Second order properties, such as correlogram function or semivariogram function, are the inputs of the so-called kriging equations. Selecting one of any useable models for the observed second order properties, such as spherical model, is not easy since the models are not based on the correlations structure of the regionalized variables. How those models being used in Applied Geostatistics can be distinguished is another important problem. One may develop many fitting models to respond to the observed second order properties of regionalized variables. However, I suggest that the model should be based on the probabilistic behavior of geologic process. The author used spherical model for copper, wolfram, and silver grades from isotropic sector (Fig. 2, 4, 3b) and exponential model for silver grades obtained along raises in isotropic sector (Fig. 3a). It seems that those semivariograms given in Fig. 3b for isotropic sector and Fig. 4 may be described by the random model implying that regionalized variables do belong to renewal process (Azun, 1983). If I knew the total number of data points used in estimation, may prove that my conclusion is correct. Recalling the test for the first order sample correlogram value, the test procedure is introduced such that the independence is rejected if [Ir(1) I > Za/2 N1/2] where Za/2 is the a/2 percentile of standard normal random variable and N is the total number of samples used in estimation (Azun, 1983). For the other observed semivariogram functions I suggest the author might try to use the so-called "Markovian model" describing not only the correlation structure of regionalized variables, but also the physical mechanism that produces the regionalized variables. The Markovian model for correlogram function is, [p (h) = T 1ih , h>1 ,] The Markovian model for the other second order properties of ReV are also derived. [T veß], in the above equation, show, for example, structural change and mineralizational variation in a considered deposit, respectively (Azun, 1983). In selecting any model, it is not easy to search for the "best" response to the observed second order properties of ReV's. The Markovian model, based on a theoretical understanding of underlying mechanism, gives more information about the occurrence of regionalized variables and respond to all properties. Random model and the so-called hole effect structure can be easily defined as a special form of the Markovian model (Azun, 1983). An estimation of any second order properties of regionalized variables may be computed through (N-1) lag. However, the dependency between the regionalized variables may be deemed to have "died out" after the so-called stationarity width (range). In practice, the estimation is carried out through 25% of the total number samples available. Therefore, the large fluctuations around the zero level and variance for correlogram or covariogram function and semivariogram function, respectively, cannot be observed. Since the number of pairs involved in the estimation of higher second order properties is small, the estimation variance at those lags is large. There is no need to show higher order estimated second order properties. After using one of any kriging procedure for block estimation, the distribution function of average grades has the same mean as the drilling sample grades but

Jan 1, 1986

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10' dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By Rudolph G. Wuerker

Charles T. Holland (Head, Dept. of Mining Engineeri*, Virginia Polytechnical Inst., Blacksburg, Va.) Mr. Wuerker has presented a very interesting discussion of the use of triaxial test methods for investigating the strength properties of rocks. Such methods, no doubt, eventually will develop considerable information of interest to those concerned with the design of mine layouts, particularly in the field of pillar design. From his discussion of my recent article, "Cause and Occurrence of Coal Mine Bumps" (Holland Mining Engineering 1958, p. 933-1002), it is evident that in one place at least I did not make my meaning clear to him and perhaps others. To clear the matter up I think it best to quote from the article, somewhat more fully than did Mr. Wuerker, as follows: "4) In actual operations — because rocksare not perfectly elastic, homogeneous, nor isotropic and because local yield does occur — the maximum stress as demonstrated by Phillips (Ref. 22, pp. 64, 65) and indicated by much experience in mining, does not occur at the walls of the opening but at a short distance inside the pillar. Furthermore, the maximum stress does not reach as great a value as theoretical considerations and laboratory experimental methods indicate.* Actual distance inside the pillar, measured from the wall, at which the maximum stress exists, has not been determined. Observations in many mines, however, indicate that this distance could have a mini-value of one to six or eight times the bed thickness and that it is probably affected by width and height of the opening, depth of cover, and relative values of the elasticity and plasticity of materials comprising the roof, floor, and coal seam. The actual value of the stress produced probably lies between the theoretical maximum and the average stress concentration that would be produced if the weight of the strata above the unsupported opening were evenly distributed over the pillars for a distance equal to the opening width." The footnote reference in the above quotation referred to the following: "*For example, the Pocahontas No. 4 coal bed in southern West Virginia is mined under cover up to 1800 ft thick. Development openings are driven 18 to 20 ft wide, and the bed is about 6 ft thick. According to the work of Panek, the tangential wall stress at mid-bed height under these conditions would reach values between 4000 and 5000 psi. Actual tests of 3-in. cubes of this coal show its compressive strength would be much less than this, perhaps as low as 400 psi. Yet the pillars usually show no evidence of failure in these headings. In this same bed at a depth of 800 ft, the author has seen an opening 225 ft between supports lying between two old groves approximately 1100 ft apart. According to the theoretical considerations, the stress in the pillar walls would have been about 18,000 psi, yet the pillar showed little or no evidence of weight. In view of these observations, it is clear that the wall stress does not attain the maximum values indicated by theory." (Underlining added to original wording.) By referring to Fig. 2A of my paper it will be noted that theoretically the maximum pillar stress would occur at the pillar wall, i.e., at the passageway surface of the pillar. Obviously this cannot be correct in the cases of stress ranging from 4000 to 18000 psi since the coal at the surface of the pillar is under no constraint and cannot have a strength much greater than 400 or 500 psi. Hence, my conclusion that the maximum stress does not occur at the wall but back in the pillar some distance from the wall. Since these stresses are pushed back in the pillar from the wall, it is also obvious that the loads transferred to the pillar from the opening will be spread over a greater area and hence Pillar stresses will not rise to the values postulated by theory and photoelastic experiment. Further since to visual inspection the coal along the pillar wall did not appear to be failed the conclusion was reached that the stress shift was caused by local elastic or plastic yield and by difference in the elastic modulus of the rocks composing the mine floor, mine roof, and coal bed. Later on under the heading "Strength of Mine Pillars" (pages 1000-1002) the effects of constraint is briefly described. Also a formula taking into account constraint is developed relating pillar strength to the uniaxial strength of coal and the L/T ratio of the pillar. Since my paper was written, reports of experiments conducted in South Africa (Denkhaus, et. al., 1959), in Sweden (Hast 19581, and in Canada (McInnes, et.al., 1959) reveal that the conclusion expressed relative to the existence of a low stress area existing around the edges of pillars and solid faces as described above is generally correct. But it seems possible that where the wall stress developed is less than the unconfined strength of the rock composing the pillar and where the roof, floor, and pillar

Jan 1, 1961

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By Roger W. Dewey

The opposition is all kinds. There are extremists. There are quiet, sensible sounding folk who can twist numbers and facts to make their point. But they are all out to shut you down! Some of them are genuinely concerned about miners' impact on the environment. Others are just anti- society, anti-big business - small is beautiful - live naturally. The opportunity for them to make those statements on television was provided by us, the Uranium Public Affairs Task Force, as part of a media tour of the State of Idaho in May. We fielded four representatives of the industry and got 25 hours of television coverage, 22 hours of radio coverage, and print coverage by every paper in Idaho. The tour included several debates, and these clips are from two of them. Our folks creamed them! This one was so upset that he ran off the set while his mike was still plugged in, trailing studio equipment behind him. But we don't always have the opportunity to rebut them. They are making these statements all the time, everywhere they can. They have learned their trade well. They use the hearing process like A1 Hirt uses the trumpet. If the process of intervention should shut us down or prevent us from getting a license, so much to the good. But even if it doesn't - they win - for it causes delay - delay costs money and so does complying with regulation. If they can make us uneconomic, and that's not too hard to do these days, they have won. Regulation restricts the decision process. Any time the decision process IS restricted, you face the possible loss of a more economic alternative. They are out to pile every regulation on you they can and every delay they can. Initiatives! They came after us - the uranium industry - in South Dakota and Montana last year. They won in Montana. We tried to reverse it in the legislature, but they were too frightened of public reaction to do it. They did put it on the ballot for reversal in November of '82. That puts it squarely up to us to influence the public so we can win a campaign. There will be more initiatives, and at local levels as well as at state. We must join together and win! The public generally supports the continued operation of nuclear power plants. They about split on whether to build more. But they strongly support regulating the industry more stringently. Every survey reflects concern about safety and the desire for the government to take responsibility and regulate. You and I know that regulation nearly always adds cost, and only sometimes increases safety. We need to influence the creation of regulation. We need to accept responsible regulation and fight that which is counter-productive. To win in hearings, to win initiatives, to win in getting responsible regulation, we need public support. We need an informed, understanding, and supportive public. To accomplish this, we need two kinds of efforts. The first is to reach the people at the local level with local representatives of our industry. Informal conversations at church, PTA, cocktail parties, whatever. Presentations to Kiwanis Clubs, League of Women Voters, church groups - wherever we can. Facts, information in printed form, to these same local audiences with the credibility of the local sources. The second is to reach mass audiences through the media. Positive media. This can be done by advertising, but it is very expensive. We have to look to influencing the reporters and editors to get more balanced and accurate reporting. We need to get free time - interviews, debates, letters to the editors, etc. The Uranium Public Affairs Task Force was created last year to provide tools for you to use to reach these audiences (it is affiliated with the Atomic Industrial Forum). Twenty-two companies provided money and man- power. A consultant, Denver Research Group, was retained to produce materials. In this Phase I effort, we first researched what issues were of greatest concern and what were felt to be the greatest needs in materials. We determined that we did not have the funds to go out and do the job for the industry, so we decided to develop tools for the Industry to go out and do the job for itself. From the research, we determined what tools we should develop for you to use. We first developed a set of the quest- ions most likely to be asked of you and the issues most likely to be thrown up to you. We have developed a loose-leaf notebook. Each page contains one of those questions or issues, a short verbatim response that you can use, a short discussion of the subject, and references you can cite or research for further information. It is organized by subject: tailings, water radiation, etc. This book is an extremely handy tool for anyone in the industry. Each uranium location should have at least one.

Jan 1, 1982