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By E. N. Cameron

GRAPHITE has been included in U. S. lists of strategic minerals since the problem of mineral deficiencies was revealed during World War I. Since 1918 the domestic graphite industry has led a precarious existence, and there has been much uncertainty as to the amounts of usable graphite of various grades that would be available from domestic sources in time of emergency. In 1950-1951 therefore, the writer, assisted by Paul L. Weis, undertook a review of domestic graphite sources for the U. S. Geological Survey.' The conclusions of this study are presented here, with a discussion of some technologic and politico-economic factors bearing upon the problem. Uses of Graphite: Natural graphite as marketed exhibits a wide range of properties, which determine the uses to which it is put. The most essential uses are in the manufacture of crucibles and related refractory articles, in lubricants and packing materials, and in the manufacture of batteries, foundry facings, pencils, and carbon brushes. Numerous specifications covering the mineral in its various applications must be met by producers and processors of graphite. The problem of supply is therefore not simply one of procuring a sufficient total tonnage, but the more difficult problem of procuring enough of each different grade to meet foreseeable needs. The amount of graphite required by American industry is not large. Ordinarily only a few thousand tons of strategic grades are consumed annually, yet the elimination of this small tonnage would have serious effects in several industries. Strategic Graphite: Since World War I, 60 to 100 pct of the country's annual supply of graphite has been furnished from imports. At present, natural amorphous graphite for use in pencils and batteries is produced largely from American-owned mines in Mexico. Graphite for foundry facings is obtained from a number of sources. Neither grade is a serious problem. High purity graphite for carbon brushes and for pencil leads, however, is imported, largely from Ceylon, in the form of amorphous lump graphite. Most of the flake graphite used for crucibles and related refractory articles is likewise imported, largely from Madagascar, and much of the lubricant and packing grade graphite used by industry is obtained from the same source. The strateg'ic grades of graphite are therefore amorphous lump of the Ceylon type, crucible flake, and flake suitable for lubricants and packing. Ceylon lump and Madagascar flake have for many years been accepted as standard by domestic consumers of graphite, and various essential manufacturing processes are geared to the use of graphite from these sources. Ceylon graphite as marketed is classified into several grades based on particle size and purity. Processing methods are said to be simple, but the products marketed are carefully graded and are consistent in their characteristics, an important matter to the consumer. Nearly all the graphite produced in Ceylon is from veins. Resources are reported to be large, labor is cheap, production costs are low, and world competition is slight—factors accounting for the commercial success of the graphite mining industry in Ceylon. Madagascar is reported to have deposits of the Ceylon type, but its output consists almost entirely of flake. Madagascar graphite as received in the U. S. is further processed by importing organizations, and a large number of grades are produced to meet industry requirements, especially those for crucible flake and for lubricant and packing grade flake. Madagascar crucible flake as marketed is noted for coarseness, uniformity, toughness, clean-

Jan 1, 1957

By Glenn C. Waterman

Richard Strong (Oliver Iron Mining Div., U. S. Steel Corp.)—Mr. Waterman states (p. 59, Trans., January 1954): "Core-sludge combining factors have been calculaied for any combination of core-sludge recovery on the basis of several logical assumptions: 1—The sludge sample loses reliability geometrically as sludge recovery drops. 2—The sludge sample should not be used if the percentage of sludge return is less than the percentage of core recovered. 3—A core sample should receive a weighting at least equal to the percentage of core recovery." Assumptions 1 and 2 seem justified at Chuquicamata and most geologists would agree to the validity of assumption 3. However, contrary to the statement quoted above, the core sample does not in general receive a weighting at least equal to the percentage of core recovery when the Chuquicamata methgd is used. Furthermore, the basic Chuquicamata method is identical to the Longyear or relative volume core-sludge assay combining method. Finally, the Chuquicamata method does not, in its present form, reflect true geometric loss in sludge sample reliability according to the relationship L = AR (N-1) The basic equations representing the two steps of the Chuquicamata method can be combined algebraically as follows (using the symbology of the original article except as noted): Vol A + B Assay 2 = ASA = Assay 1 Vol A VolB Core Assay [I] Vol A CA.F + ASA (100 —F) Combined grade =[21 100 Pct where F and (100 — F) are the core and adjusted sludge assay factors from Fig. 3. Substituting Eqs. 1 and 2 and collecting terms Combined grade = Vol B Vol A + B CAF (100—-F) + Assay 1 (100-F) Vol A Vol A 100 pct Eq. 3 is a unified and general statement of the Chuquicamata method. The true core factor includes not only the factor F from Fig. 3 but also the quantity VolB ------------- (100 — F), which is implicit in the value of Vol A the adjusted sludge assay. This quantity is real and positive for all values of F and core recovery less than 100. Therefore the true core factor is always less than F except when F is equal to 100. If sludge recovery is 100 pct, Eq. 3 can be further simplified as follows: Let F = percentage of core recovered. Let Vol A = Vdh (100 Pct — Pct CR) where Vdh is the total volume of the sampled interval and let Vol B = (Vdh — Vc.) Pct CR where V, is the core volume in the sampled interval at 100 pct core recovery. Then combined grade = Vo V. CA Pct CR- + Assay 1, 100 Pct — Pct CR Vdh Vdh [4] 100 Pct Eq. 4 shows that when sludge recovery is 100 pct the laboratory sludge assay receives significant weight in the Chuquicamata method, even at 100 pct core recovery. The maximum weight assigned to the laboratory sludge assay depends on drillhole size, as follows: Eq. 4, with suitable changes in symbology, is identical to Royce's formula 8,' which is a statement of the Longyear or relative volume method of combining core and sludge assays. If Mr. Waterman's assumption 3 is of paramount concern to the geologist, the Royce method (for core recoveries of 60 pct and above) or a method employing the percentage of core recovered as a core weighting factor are the only recognized methods known to the writer which achieve the desired result. A modification of the latter method embodying Mr. Waterman's assumptions 1 and 2 would result from applying the factors from Fig. 3 directly to the laboratory core and sludge assays.

Jan 1, 1956

air-lift and equipped with tapered tubing of proper design, we would have a gas input consumption of about 2500 cu. ft. per bbl., which at 3 to 4c. per 1000 cu. ft. would be 7 1/2 to l0c, per bbl., and there would be very infrequent loss of production due to stoppages. It has been demonstrated that with efficient design of air-gas lift, the production of wells can be increased much beyond that obtained with the former type of air-lift employed; also that small wells can be operated by air-lift with tapered tubing at a cost that places this method in competition with beam pumps in many fields. The next step in conservation that the writer expects to have an opportunity to demonstrate is that of restoring the pressure in a pool and producing by air-gas lift all of the oil possible to lift economically. This combined operation is probably the method toward which we shall eventually be working in recovering the maximum quantity of oil from pools where the oil is recovered through bore holes. General Discussion on the Air-gas Lift H. P. Porter, Tulsa, 0kla.—The papers presented at this meeting contain a great amount of valuable information. Wonderful progress has been shown in the development of air and gas-lifts. There has been nearly everything brought out that touches upon the subject. The real point that is lacking is exact knowledge of the velocity with in the flow column which will produce the best effect—that is the thing we must know more about. Velocity in Gas-lift Flow In other lines of industry the matter of velocity of fluids in pipe lines has been well analyzed and there are known laws by which to calculate velocity of flow; for instance, in irrigation work large pumps are designed with intake pipos to employ an intake velocity of 4 ft. per scc. By reduced cross-sect'ion the velocity is increased rapidly as it enters the pump and the discharge rate is at 12 ft. per src., which in turn is reduced in the discharge column to 4 ft. per sec. Crushed coal, grain and granular material is found to be best conveyed by air when a pneumatic conveyor is employed at 100 ft. per sec. As in the design of a pumping plant or a pneumatic conveyor, the velocity at the lower end of the column in the flowing well must be controlled within certain limits for best results. Mr. Griswold, I believe, stated that they had velocity as low as 15 it. per scc. and from that up to 78 ft. per sec. Mr. Pierce and Mr. Lewis showed an ideal flow column showing how the velocity increased as the fluid was carried up the column, hut did not give any figures as to the velocity. It would be well to take that sort of a diagram to establish an ideal velocity at the lower or intake end, and then calculate the velocity from expansion of the gas as it goes up. It may be that the, ideal intake velocity would vary, depending on the depth of the well, the quantity of liquid to be handled or the pressure which it may be desired to hold. The subject is one that might be worth much research.

Jan 1, 1928

By A. M. Rowe

A considerable quantity of experimental hydrocarbon K-factor data has been correlated as a function of component identity, temperature, pressure and convergence pressure. To utilize these correlations effectively, convergence pressure must be determined accurately, particularly for volatile mixtures near their critical states. This paper presents phase diagrams that illustrate physically the meaning of convergence pressure. A new method, referred to hereafter as the "critical composition method", will be outlined for calculating convergence pressure. An example calculation has been included to illustrate how to use this new technique. INTRODUCTION The principle of hydrocarbon phase composition calculations as applied to such diverse problems as optimizing separator performance or predicting fluid compositions at various stages of reservoir depletion is the same. Usually, temperature, pressure and the numbers of moles of the various components of the fluid contained in a given volume are known. Questions answered by the phase calculation are what fraction of the total mass of fluid exists in each of the equilibrium phases, and what are the mole fractions of the various components in the two phases? To answer these questions the Natural Gasoline Supplymen's Assoc. (NGSMA) has correlated a considerable quantity of K-factor data as a function of temperature, pressure, component identity and convergence pressure.l To use these correlations to obtain the best answers possible, one must be able to calculate the convergence pressure. This is particularly true for over-all fluid compositions in the neighborhood of the critical state. STATEMENT OF THEORY Use of convergence pressure as a correlating parameter is based on a postulate similar to the law of corresponding states used in correlating PVT data of hydrocarbon gases. This postulate, which proposes convergence pressure as a correlating parameter, has been stated as follows: "The equilibrium vaporization constant for one component in a complex system is the same as the equilibrium constant at the same temperature and pressure for the same number or kind of components, providing only that the convergence pressures of the two systems are exactly the same at the same temperature and that the components are of the same homologous series".2 This law, as with all laws of physics, cannot be proven theoretically. It can only be justified by experimental data supporting its premises. Arguments have been made that this law violates Gibb's phase rule. For example, consider a four-component system. By Gibb's phase rule, which is thermodynamically rigorous, f = c — P + 2 =4, for a four-component, two-phase system. Thus, four independent intensive variables must be specified to establish completely all the intensive variables of the equilibrium phases. On the other hand, according to convergence pressure theory, only three variables need be specified for any mixture containing four different components. These variables are temperature, pressure and convergence pressure. Thus, the two laws appear to be in conflict. However, the convergence pressure postulate is more restrictive than Gibb's phase rule. It applies only to mixtures of the same homologous series. Hence, these two concepts are not in disagreement. PHASE DIAGRAMS DESCRIBING CONVERGENCE PRESSURE This paper presents phase diagrams grading from the simple two-component system to the more complex four-component system to illustrate convergence pressure. A less abstract definition of convergence pressure will be stated that is

By E. P. Miesch, P. B. Crawford

A study was made of the effect of permeable and impermeable lenses in a reservoir on the production capacity of a well. Both steady-state and unsteady-state data were obtained. An electrical resistivity model was used to obtain the steady-state data and thermal models. were constructed to obtain the unsteady-state data. The productivity of a well is affected very greatly only when the lenses are close to the well. The effect of circular lenses on the productivity ratio can be correlated with the distance from the center of the lens to the center of the well divided by the radius of the lens. When this dimensionless distance is equal to six or greater, the effect of the lenses on production capacity will be negligible. The pseudo steady-state productivity of a heterogeneous reservoir can be predicted using steady-state data. INTRODUCTION Many analytical solutions of reservoir behavior assume that reservoir rock is uniform and homogeneous. Although this assumption is used, all of the data from core analyses and well logging indicate that the reservoirs are heterogeneous. Very little work has been done on the performance of heterogeneous reservoirs. The work of Landrum,l et al. showed that transient phenomena in oil reservoirs could be studied with thermal models. Pickering and Cotman2 used thermal models to study flow in stratified reservoirs and investigated the effect of inhomo-geneities in oil reservoirs on transient flow performance. Loucks3 made a mathematical study of the pressure build-up in a system composed of two concentric regions of different permeability. Root, Silberberg and Pirson4 studied the effect of the growth of the flooded region on water influx predictions using a thermal model consisting of three concentric cylindrical regions of different thermal properties which simulated the aquifer, the flooded region and the unflooded portion of the original hydrocarbon region. Tomme, et a1.5 made a mathematical study of vertical fractures. The object of this investigation was to study the effect of highly permeable and impermeable lenses in the vicinity of the wellbore on the pressure depletion history of the well. Steady-state data were obtained for both conductive and nonconductive lenses that completely penetrated the formation. The lenses were symmetrically located at various distances from the wellbore. The unsteady-state data were obtained on seven thermal models. EXPERIMENTAL EQUIPMENT AND PROCEDURE STEADY-STATE DATA The steady-state data were obtained from an electrical resistivity model 30 in. in diameter and approximately 11/2 in. deep. The outside of the model was lined with a 30-in. diameter copper strip, which served as the outer boundary of the reservoir. The bottom was covered with a sheet of plexiglass so that it would be nonconductive. The model was filled with a slightly saline solution. The well size was varied from an 0.064-in. diameter copper wire to a 10-in. diameter copper cylinder. Readings were taken with an impedance bridge using AC current to prevent polarization at the contacts. Copper and wax lenses were used to represent infinitely conductive and nonconductive lenses, respectively. The resistance was first measured for each well diameter with no lenses in the reservoir. Then the conductive and nonconductive lenses were spaced symmetrically at various distances from the well and the resistance read from each lens location. The diameters of the conductive lenses were 3, 1.022 and 0.624 in., and those of the nonconductive lenses were 3, 2.25 and 1.563 in. The ratio of each resistance reading to the resistance reading with no lenses in the reservoir

Jan 1, 1965

By J. A. Snyder, W. L. Finlay

G. Edmunds—Solid solubility is considered to be of either the interstitial or the substitutional type. Is it possible, in a binary alloy as the simplest case, that some of the solute atoms are present in the normal lattice sites (substitutionally or filling lattice vacancies) while simultaneously others are in interstitial positionss One might even ask whether a distribution of the two types may be the normal situation. H. M. Meyer—Metastable states of interstitial atoms occupying vacant lattice sites possibly occur as well as of substitutional atoms squeezed in between regular matrix positions. However (as we know since Hume-Rothery), the solute atoms choose between the two kinds of solutions; consequently, every solute will be unequivocally either substitutional or interstitial in the equilibrium state of the solid solution. M. Balicki—In view of the fact that the authors apparently correlate the analysis of the alloys at the ingot stage with the properties exhibited at the testing stage, I would like to ask whether this is a fully justifiable procedure. In other words, how good are their determinations of solute concentration for correlating them with the mechanical properties. The answer to this question may explain some of the divergencies. Assuming good enough homogenization of the samples and exact determination of mechanical properties the position of the plotted experimental points will depend solely upon the accuracy of composition determination. If this is not accurate, say due to loss or pickup of elements during processing from the ingot to the testing stage, or due to a systematic error in the method employed for obtaining solute concentration data, the points will deviate from their true position and may align themselves along a different curve than the one expected. H. V. Kinsey—We have been studying the creep-rupture properties of titanium-base alloys at 1000°F. In the course of this work, anomalies in behavior of the alloys that would suggest that the material under test was becoming stronger as the test progressed have been observed. If this was so, the most likely explanation that we could think of was that the test bars were absorbing oxygen and nitrogen from the air during the test and were thereby becoming strengthened. In an attempt to determine the strengthening effect of absorbed oxygen and nitrogen the following experiment was conducted. A length of cold-rolled titanium was supplied by the E. I. du Pont Co. Two test bars, having a 1/4 in. diam gauge length, were prepared from this material. One bar was tested in the as-received condition. The second bar was heated in air at 1550°F for 100 hr and subsequently air cooled prior to testing. A testing temperature of 1000°F was employed. The results of these tests are tabulated in table 11. In the author's opinion, is it reasonable to assume that the bar that was exposed to air at 1550°F for 100 hr was stronger because it absorbed oxygen and nitrogen from the air during this heat treatment? W. L. Finlay (authors' reply)—Direct experimental evidence for or against Mr. Edmunds' interesting suggestion will probably never be available. It seems possible, however, that mixed interstitial-substitutional solid solution might well occur with interstitial elements. The less likely possibility of interstitial solution of a normally substitutional element like copper in aluminum was recently discussed at length by the

Jan 1, 1951

By S. S. Shen, M. J. Pool, P. J. Spencer, J. R. Guadagno

VERY few thermodynamic data are available for rare-earth alloys, partly because of the difficulties of obtaining the metals in sufficiently pure form and also because of their comparative scarcity up to the present time. The rare earths form a very interesting series in the periodic table in view of the progressive filling of their 4f subvalence electron shell and would be expected to provide useful information with regard to alloying characteristics of transition elements. It has been found in recent calorimetric investigations that the heats of solution of a number of the rare-earth metals in liquid tin are highly exothermic.1-4 Exceptionally strong bonding between rare-earth and tin atoms is clearly indicated in the liquid solutions. Continued thermodynamic studies of the behavior of rare earths in solution could thus contribute a great deal to present theoretical knowledge of alloying behavior and would yield an insight into bonding of a strength hitherto unencountered in liquid alloys. The determination of the heats of solution of the pure components in liquid tin is an essential preliminary to calorimetric work of this nature. Heats of solution of praseodymium, neodymium, and samarium in liquid tin at 750" ' and the heats of mixing of Pr-Nd solid solutions' have already been determined in this laboratory. The present investigations with lanthanum continue the study of rare-earth elements. Details of the construction and operation of the liquid metal solution calorimeter used in this work have been published previously by Pool and Peluso and no further description will be given here. The lanthanum used in heat of solution determinations was supplied by Lunex who quoted the purity as 99.9 pct. Their detailed analysis of the material is given in Table I. Samples of 0.0003 to 0.0005 g-atom were used for each run and great care was taken to remove all surface oxide prior to weighing. The samples were stored at all other times in a beaker of oil to prevent their otherwise rapid oxidation. The compounds LaSn (Cudu, L1P type structure) and La&, (structure not classified) were prepared from the appropriate quantities of the two pure components by arc melting under a purified argon atmosphere and once again great precautions were taken to avoid any subsequent oxidation of the specimens. Although no structural examination of the compounds was made, the consistency of thermodynarnic measurements carried out on twenty or so individual samples of each indicates that the compounds were in fact homogeneous, single phase alloys. Samples of the compounds consisting of 0.0003 to 0.002 moles were used in the calorimetric measurements. A solvent bath consisting of approximately 80 g of 99.9 pct pure Sn was used for each series of runs and its heat capacity was determined at regular intervals throughout the experiments using pure tin or tungsten calibration samples. Measurements were made of the heat of solution of lanthanum in liquid tin at 725", 750C, and 775°K and at compositions up to 2.21, 4.76, and 5.25 at. pct La at the three temperatures respectively. In every case, the heat of solution of lanthanum remained constant at its limiting value, within experimental limits, up to the highest lanthanum concentration investigated. Since no change in was observed, it was concluded that the liquid/liquid + LaSn, phase boundary had not been

Jan 1, 1969

By Joseph G. Franzone, Alan K. Kuhn, Jerry J. Oliver

INTRODUCTION Tailings produced by many uranium milling operations consist of fine sands with some silt and slimes. When fine sandy materials are placed by hydraulic methods behind an impermeable dam, they are deposited in a loose state and some portion remains saturated. These saturated, loose fine sands are highly susceptible to liquefaction, the phenomenon in which a monotonic or cyclic disturbance causes excess pore water pressure and, concurrently, a total loss of strength in the sand. Once liquefied, the fine sand flows, causing collapse of supported structures. The potential for such a liquefaction failure was identified and successfully treated at Sohio Western Mining Company's L-Bar Uranium Operations near Seboyeta, New Mexico. The Sohio tailings dam is an earthfill starter dam with tailings raises constructed upstream of the starter dam crest. Beginning with the start of mill operations in 1976, tailings were deposited hydraulically in the impoundment behind the starter dam. As the tailings level approached the crest of the starter dam, beached tailings were excavated and placed in lifts by a dozer to form two raises above the crest of the starter dam. As the impoundment has gradually filled with tailings, the decant water pond level has risen. Correspondingly, the water level in the tailings dam, upstream of the chimney drain, has also risen. By August 1980, the phreatic surface was above the crest of the starter dam and stability analyses indicated that the tailings dam did not have the safety factor of 1.0, under static loading with liquefaction, implicit in the 1980 New Mexico State Engineer's requirements. The problem related directly to the high phreatic surface in the loose sandy tailings behind a dam structure that was not capable of resisting failure which might develop in liquefied tailings. Two methods of stability enhancement were considered for the Sohio dam. One method was reinforcement of the dam using a clay buttress placed against the downstream slope. The other method was installation of horizontal drains through the starter dam to drain decant water and lower the phreatic surface. Either method would increase the stability of the dam. However, the comparative analysis of the methods indicated that horizontal drainage offered significant advantages in cost and could provide a more direct remedy of the source of the problem, the saturated section of tailings. In addition, a drainage system would be more amenable to modification and more quickly installed than a buttress. On the other hand, a clay buttress could be more directly controlled, would involve routine earthwork, and has successful precedent. Therefore, the buttress approach would involve less risk. After weighing the advantages of both methods and the costs versus risks, the horizontal drainage approach was selected. Consequently, a horizontal pipe drain system was recommended and designed (D’Appolonia, 1981a). This paper describes the design and installation of the drainage system and its initial performance. PIPE DRAIN SYSTEM DESIGN Design Criteria and Parameters To increase the stability of the dam to acceptable levels, the drainage system had to lower the phreatic surface behind the dam to the level calculated to give a minimum safety factor of 1.0 under conditions of liquefaction. In addition, the system needed to be essentially self-operating, easy to maintain, and economical. To accomplish these objectives, the following design criteria were established: 1. The pipe drains must lower the phreatic surface at least 4.3 m (14 ft.) at the midpoint along the dam (the deepest section) and by proportionately smaller amounts toward the abutments to satisfy safety factor requirements.

Jan 1, 1982

By C. Perez-Rosales

A simplified method for evaluating specific surface of porous media is described. The theory takes as its point of departure a previous statistical method. Due to its simplicity, it is considered that the proposed method has certain advantages over methods currently used. By making some simplifications, the procedure for estimating specific surface is reduced to superposing, on an enlarged reproduction of a section of the sample to be analyzed, an evenly spaced grid and counting the number of intersections of the grid lines with the perimeter of pores. An indirect test of the theory is presented and the advantages of the method are discussed. INTRODUCTION The specific surface of a porous medium, defined as the surface area of the pores per unit bulk volume, is an important parameter with regard to flow of fluids through porous materials. In particular, it has long been recognized that specific surface is closely related to permeability. Since the internal surface of any porous material is extremely complex, the measurement of specific surface can only be accomplished by indirect means. It is considered that the best method' in current use for determining specific surface is the statistical method of Chalkley, Cornfield and Parka who originally applied it for estimating volume-surface ratios of morphologic components, such as cells or nuclei. This method will be outlined later. A method which has been used extensively in determining specific surface is based on the adsorption of a vapor by the internal surface of porous media. However, this method does not yield the surface pertinent to fluid flow, since it includes the tiny molecular interstices which do not influence the permeability of the porous material.' This method has been employed by Brooks and Purcell measure internal surface area of sedimentary rocks. The Kozeny equation, which relates the specific surface to the permeability of a porous medium, has found wide use in determination of specific surface. However, the KOzeny equation is not strictly correct. Large discrepancies have been found between theory and experiments.' Consequently. the specific surface estimated by this method is subject to serious uncertainties. Finally, there are other methods for specific surface measurements which are based upon a variety of physical and chemical properties: the heat conduction by a gas, ionic adsorption phenomena and direct chemical reactions of the surface with other substances. This paper describes a simplified statistical method for determining specific surface of porous materials. It is considered that, due to its simplicity, it has certain advantages over the methods presently used. For its validity, it is required that the porous structure of the material under study be of a spatially random nature. This is not a serious limitation since the naturally occurring porous media have this characteristic. THEORY The method proposed in this paper takes as its point of departure the interesting result obtained by Chalkley et al The method shows that if a line of length r is dropped repeatedly at random over a section of a porous medium, and counts are made of the number of times the two end points fall within pore areas (denoted by h for "hits") and the number of times the line intersects the perimeter of pores (denoted by c for "cuts"), then in a very large number of throws where S is the internal surface of the sample (surface of pores) and V, the volume of the pores (Fig. 1). Since the specific surface S, and the porosity 4 are given, respectively, by S. = Sl V, and 4 = V,l V,, where V, is the total volume of the sample, it follows from Eq. 1

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki's phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki's data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By Raymond B. Ladoo

Wollastonite is a calcium metasilicate, with the formula CaSiO3; containing theoretically 48.3 pct CaO and 51.7 pct Si02. It is one of many natural and synthetic silicates with varying CaO/SiO2 ratios, with and without water of crystallization. While it is a very common mineral, deposits of sufficient size and purity to be of commercial interest are unusual. There is only one producer (1958) of wollastonite for industrial use in the United States, Godfrey L. Cabot, Inc. at Willsboro, New York. There has been a small production of surface material for ornamental use from near Blythe, California. Carload tests have been made on California wollastonite for making mineral wool and a commercial plant for this purpose was projected in 1957. Properties Wollastonite is monoclinic and commonly occurs in masses or aggregates of bladed or needle-like crystals. It has a perfect cleavage parallel to the long prismatic axis. It is rather brittle and some types grind easily to a very finely fibrous product, but other types, due to interlacing of fibers, are tough and difficult to grind. Mobs hardness is 4.5 to 5; specific gravity 2.8-2.9; index of refraction 1.616 to 1.631; melting point 1,512°C. Color when pure is a brilliant white, but when less pure it may be gray or brown. Luster is vitreous, transparent to translucent. Common mineral associates are garnet (several varieties), diopside, calcite and quartz. The nature of the mineral impurities determines to a large degree the commercial value of a deposit. At Willsboro, New York, the impurities consist chiefly of iron garnet and iron diopside which are both magnetic and so are easily removable by magnetic separation, yielding a nearly theoretically pure product. Some deposits in California contain calcite and quartz which cannot be removed cheaply, thus limiting market possibilities. Occurrence Wollastonite is a contact metamorphic mineral occurring in most places within or associated with impure limestones. The deposits at Willsboro, New York1,2,3,5 consist of two or more beds dipping 15-50°E and striking NW-SE. The main bed, 30 to 70 ft thick, may be traced on the surface for at least 2 ½ miles. In this belt, the Pre-Cambrian Grenville limestone has been injected and partially replaced by the more liquid portions of an anorthositic magma. Buddington and Whitcomb3 have described the rock as "Mixed gneisses, pyroxenite and garnetiferous gneisses and skarns." Prospecting revealed the wollastonite at ten different places in the belt, overlain in most places by a garnet rock. Diamond drilling has proven several million tons with probable reserves around 15 million tons. Interbedded with the wollastonite are beds of garnet from a few inches to several feet in thickness. In the wollastonite ore itself the chief and almost only associated minerals are garnet (mostly almandite but some andradite and grossularite) with small amounts of green hedenbergite. Inasmuch as the almandite and diopside are magnetic they are easily separated from the wollastonite in high intensity magnetic separators. If grossularite should occur in quantity other means of separation would be needed. Wollastonite has been reported at 35 localities in California12 but only those in the Big Maria and Little Maria Mountains, 16 to 20 miles north of Blythe, Riverside County, are

Jan 1, 1960

By F. W. Jessen, R. W. Durie

The dissolution of salt in the development of salt cavities is controlled by free-convection boundary layer flow along the salt surfaces. It is the purpose of this paper to expand upon results published previously, and primarily to illustrate the influence of surface features on the boundary layer and hence the dissolution process in the development of underground salt cavities. General dissolution equations are presented that apply to a surface inclined to the vertical. A salt surface inclined so as to be overlain by water is dissolved by boundary layer flow, while an inverted surface is dissolved by a combination of boundary layer and cellular flow. Detailed investigation of the boundary layer was limited to laminar free-convection flow. Truly laminar free-convection boundary layer flow may be encountered only in laboratory solution cavities, but the boundary layer will control dissolution even where cavity dimensions are such that free-convection turbulence will occur. The factors found to significantly affect the laminar boundary layer will affect dissolution with a turbulent boundary layer. INTRODUCTION Underground salt cavities have been used extensively for the storage of LPG products, and the use of these cavities is expanding each year. The increasing requirements for such cavities suggest the need for a better understanding of the mechanisms involved, for the purpose of the control of cavity geometry and the most effective use of the injected water. A previous paper outlined a quantitative approach to the determination of salt dissolution rates in the laminar free-convection dissolution of salt. It is the purpose of this paper to expand upon the results previously published and to point out significant factors in the application of these results to the dissolution of field cavities. The dissolution of salt in laboratory scale cavities is controlled by the free-convection boundary layer, which is the region of flow along the salt surface caused by the difference in buoyancy forces resulting from the salt dissolution. The transfer of salt into solution at the salt face causes an increase in salinity, and hence a greater density, in the water at the salt surface. The region of higher density tends to fall through the lighter, less saline water and a flowing boundary layer is the result. The water remains stationary at the contact with the salt surface,l so the resulting velocity profile is such that the influence of gravity is opposed by a viscous shear force at the salt surface. For salt to be transferred into solution from a solid surface to a boundary layer of fluid, it must diffuse through a stationary film of water at the salt contact. According to Fick's first law, the rate of mass transfer by diffusion is the product of the diffusion coefficient and the concentration gradient, with diffusion transfer in the direction of decreasing salinity. Once the salt has passed into the boundary layer, it will be transferred by a combination of molecular diffusion and convection. The convection transfer will in turn affect the rate of dissolution by influencing the gradient of the salt concentration at the surface. In the previous investigation by the authors to determine the basic mechanism of the salt dissolution process, an equation was developed that agreed very well with the experimental rates of free-convection salt dissolution from a smooth vertical surface. The technique was taken from the work of Eckert2 in the analogous heat transfer system and will be referred to as the integral method. The rate of salt transfer from a vertical section of height H was found to be:

Jan 1, 1965

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE existence of v phase in the Mn-Mo system was discovered in this laboratory several years ago,' but neither the conditions of its formation nor its composition were known, and preliminary attempts to reproduce the phase were unsuccessful. We wish now to specify the information appropriate to phase formation on the basis of experiments performed since that time. The starting materials were in every case electrolytic manganese and high purity molybdenum. Two methods of preparation were employed: l—arc-melting varying combinations of the elements in an inert atmosphere and subsequent heat treating, and 2—sintering compressed mixtures of finely divided powders of the elements. In the latter method, the powders were first passed through 200 mesh screen and then compressed into cylinders of % in. diameter and % in. length, which were sintered at elevated temperatures in an atmosphere of dry hydrogen. For some samples, the sintering temperature was 1200°C (for 1 hr), and these were then heat- treated at lower temperatures for times up to 24 hr. Eventually it was found, for the proper composition, that essentially pure a phase could be produced by sintering at 1125°C for 3 hr. Quenching to room temperature was effected by means of a stream of cold, dry hydrogen in a water-cooled chamber. The arc-melting procedure was found to be unsatisfactory after an investigation of many samples at different compositions and temperatures. Large quantities of manganese were vaporized during melting and none of the products were homogeneous or contained extended regions of pure phase. Nonetheless, these experiments established that no formation occurs in the Mn-Mo system below 1115oC, and indicated, at least roughly, the composition range of interest for further exploration. The more definite results obtained from samples produced by the second method are given in Table I. A portion of sample 2 heated for 16 hr at 1000°C in a Vycor tube transformed to molybdenum plus unidentified phases of complex X-ray pattern. From these few results it appears that the region of phase is quite narrow in composition. It is of interest that the composition is such as to make for difficulties in correlating this structure on an electron atom basis with other a structures of iron, cobalt, and nickel. In that respect Mn-Mo shows the same anomaly as Mn-Cr and Mn-V systems.' A second feature is that in common with the two other known molybdenum (Fe-Mo and Co-Mo), Mn-Mo v exists only at elevated temperatures. The X-ray powder pattern of the pure a phase of Mn-Mo is given in Table 11. It agrees well with the patterns established for other structures, especially with that for Fe-Mo as given by Goldschmidt.An attempt is being made to establish whether an ordering of the respective atoms occurs and such information will be reported in a future publication. Acknowledgment The authors acknowledge gratefully the assistance of Mrs. J. R. Belanger in some portions of this work. References 'J. S. Kasper, B. F. Decker, and J. R. Belanger: Journal of Applied Physics (1951) 22, p. 361. 2 A. H. Sully: Journal Inst. Metals (1951) 80, p. 173. H. J. Goldschmidt: Research (1949) 2, p. 343.

Jan 1, 1954

By R. B. Ladoo, C. A. Stokes, R. N. Secord, A. L. Hall

INDUSTRIAL mineral history shows that the entrance of new, nonmetallic minerals into commercial production can be expected to occur from time to time. Latest entrant into the field is wollastonite. Except for one short-lived period in Kern County, Calif., starting in 1933, wollastonite has never before been produced on a commercial scale. But the signs are up for its entrance as an economic factor in the mineral market. Small scale experimental production from a deposit near Willsboro, N. Y., started about 1943. A pilot plant was built in 1949-50 and irregular, small scale, production has continued. In early 1951 Godfrey L. Cabot, Inc. of Boston, world's largest producer of carbon black, took an operational lease on the property to study the deposits and make market surveys. This became Cabot's first venture in the mineral field, when they took over operations and began design of a new mill, expected in production in 1953. Properties The properties and major uses of wollastonite are comparable to New York fibrous talc. It has about the same specific gravity and index of refraction as talc, but is somewhat whiter and softer. The two most important fields of use, paint and ceramics, are the same as for talc. Ground wollastonite has a fiber length as much as 13 to 15 times the diameter. This particular property makes it applicable in the paint field and others. In addition, the length-diameter ratio may be controlled to rather narrow limits by choice of grinding method. Another important commercial property is brightness or whiteness. Wollastonite reads from 92 to 96 pct of MgO on the G.E. brightness meter for a 99 pct -325 mesh grind. Purity and uniformity of product are important. Chemically, the wollastonite now being mined analyzes SiO2 51.76, CaO 47.56, FeO 0.46, MnO 0.04, and H2O 0.09 pct. Theoretically pure wollastonite analyzes SiO2 51.75 and CaO 48.25 pct. This analysis indicates over 98 pct calcium silicate, with only small amounts of contaminating ingredients. That these ingredients are not detrimental to color or brightness is shown by the high brightness value of the fine ground material. [ ] By-product calcium silicate from electric furnace production of phosphoric acid has little physical re-semblance. to this wollastonite, being an off color white, and lacking in fibrous crystalline character. Minerology Wollastonite is a calcium metasilicate, CaSiO3, a white, medium hard, fibrous mineral. In this deposit wollastonite occurs as well crystallized aggregates of bladed crystals intergrown with garnet, and with a few percent of green diopside. The beneficiated product is about 75 pct wollastonite, 15 pct garnet, and 10 pct waste, largely middling. Wollastonite-garnet ore occurs in at least two beds. The main bed, varying in true thickness from 30 to 70 ft, dips into the hill at an average 30° and is enclosed in gneisses. Diamond drilling has proven the orebody to an average depth of 200 ft along 2000 ft of outcrop with adequate tonnage for many years of quarry operation. The wollastonite-garnet ratio varies locally, but average composition is uniform over long distances. A friable ore, it is easy to drill, shoot, and crush. Beneficiation Unlike talc this ore has to be beneficiated. Successful treatment depends upon the fact that it contains virtually nothing but wollastonite, garnet and a minor percentage of diopside. A very pure wollastonite product can be made by high intensity magnetic and/or gravity separation methods.

Jan 1, 1952

By T. C. Russell

The Conda phosphate mine, eight miles north of Soda Springs in Caribou County, Idaho, was opened up by the Anaconda Copper Mining CO. in 1920. Except for brief periods, during the 20's and early 30's, the mine has maintained a continuous production, and 2,100,000 short tons of phosphate rock have been shipped to the company's phosphate fertilizer manufacturing plant at Anaconda, Mont., or to independent processing plants on the Pacific Coast; a small tonnage of the rock has been shipped to the Hawaiian Islands. The Phosphoria formation on the Conda property consists of two, commercial-grade phosphate beds separated by 147 ft of black to brownish colored phosphatic calcareous shales interbedded with softer mudstones, clays, and occasional narrow seams of oolitic phosphate. The main lower phosphate bed in the series averaging 7.1 ft in thickness, is called the "foot-wall bed," which lies coriformably on the Wells limestone formation, the 1atter often containing irregular bands of chert. The upper or " hanging-wall bed" of phosphate rock averaging 7.2 ft in thickness, is overlaid by thick quartzite beds, locally called the " Rex chert" member in the upper portion of the Phosphoria formation. (Fig 1.) There are two anticlines on the property with axis striking approximately parallel to the mountain range beneath which extensive development on phosphate rock has been conducted in the past, and is now in progress. The phosphate beds have been eroded to a large extent from the tops of these anticlines, leaving at least three well-pronounced outcrops of the phosphate beds exposed within the boundaries of the Anaconda Copper Mining Cornpany's properties. At present, mining operations in the Conda No. 3 mine are confined to the two phosphate beds along the east flank of the easternmost anticline, where the dips on the beds vary from 50° to 60° east, thereby affording favorable conditions for the sublevel mining system now in use. Mining operations formerly were confined to the footwall or lower oolitic phosphate bed because of its higher phosphate and vanadium contents (32 pct P²O5 and 0.29 pct V2 O 5); this bed averages 7.1 ft in thickness. The oolitic portions of the upper bed were of satisfactory grade, but the shale and clay partings (Fig 2) diluted the mined rock and could not he separated economically by selective mining or by sorting. Experiments in beneficiating this rock were carried on for a number of years. Recently, a simple washing process was adopted, which gave a satisfactory grade of concentrates and a high recovery of P² O5. In 1947 it was decided to expand Anaconda's production of treble superphosphate and phosphoric acid by approximately 90 pct. This rock will be obtained from the footwall and hanging-wall beds, and the rock from the hanging-wall bed will be benefici-ated at -Anaconda.l In order to take advantage of the previous development on the 500 secondary haulage level, short crosscuts will be driven at approximately 950 ft intervals from the existing lateral drifts through the hanging-wall shale beds. From the inner end of each crosscut, short lateral drifts will he driven in both directions, so that four working raises can he put up on the dip of the phosphate bed at proper intervals along each of the lateral drifts. The mining operation on the footwall bed at Conda

Jan 1, 1950

By G. Y. Chin, M. T. Dolan, W. L. Mammel

We have obtained by computer methods the solutions of the Taylor analysis1 for axisymmetric flow in bcc metals. Four modes of slip have been treated in detail:2-4 (111), {112}(111), {123}( 111), and a mixture of all three. In addition to obtaining anisotropy of strength data for randomly oriented or textured polycrystalline material,4 we have also obtained the lattice rotation resulting from slip on the predicted systems. The patterns of lattice rotation are essential to an improved understanding of texture development during deformation. The present note shows the results of lattice rotation for 5 pct axisymmetric compression, for fifty-two axial orientations distributed at 5-deg intervals throughout the standard stereographic triangle. The data are presented in Figs. 1 to 4 for the four modes of slip. The lattice rotation is indicated by a vector, the ends of which correspond to the positions before and after the deformation. The different vectors emanated from a given orientation represent different combinations of five slip systems that satisfy Taylor&apos;s minimum shear criterion.&apos; Fig. 1 shows the results for {110}< 111> slip. They are similar to those obtained by Bishop5 for the case of (111 )(110) slip in axisymrnetric tension, since in axisymmetric flow the sense of lattice rotation for {111)( 110) in tension is the same as that for (110) (111) in compression. The pattern of lattice rotation may be divided into three regions: region A in which the rotation is toward [100]; region B, toward [lll]; and region C, toward either [ loo] or L lll]. Although some slip combinations in region C lead to [1101, the latter is not stable as continued activity of the same combinations will eventually move the axis toward [loo] or Llll]. It may also be noted that [loo] is itself not stable. However, close inspection of the vectors in region A shows that it is impossible for an axial orientation within A to rotate outside its boundary. Hence after heavy compression, all orientations from A and some from C are expected to form a diffuse band in the [100] vicinity. By far the largest region is B. Here all orientations rotate to [lll], which is a truly stable position. Thus the [111] texture component is expected to be rather sharp. For the case of (112 }( 111) slip, Fig. 2, region C is enlarged at the expense of A, with B about the same as for {110}( 111) slip. A significant difference, however, is that [loo], as well as [Ill], is now truly stable. Fig. 3 shows the results of slip on {123}( 111) systems. Region B is substantially enlarged at the expense of C, with A being intermediate in size between the {110}(111) and {112}(111) cases. Like the case of {110)( 111) slip, [100] is itself unstable. However, the lattice rotations here are confined to less than 5 deg; hence it may be considered "stable" for practical purposes. Finally, Fig. 4 shows the results of mixed slip. Here region B is the largest, and C the smallest, of all the cases considered. Both [loo] and [ill] are stable. The behavior of the three corner positions is, in fact, identical to the case of {112)( 111) slip, Fig. 2; it turns out that in these positions for the mixed slip case, all the active slip systems (based on Taylor&apos;s criterion) belong to pure {112}( 111) .4 In summing up the results for the four modes of

Jan 1, 1968

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,&apos; petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-&apos;I2 increases (where d is the grain diameter). These results can be understood in terms of Petch&apos;s analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.&apos; The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast&apos; reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By W. Philippoff, Donald E. Cadwell, S. R. B. Cooke

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953