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By M. E. de Morton

Recovery and early recrystallization of heavily deformed, 99.98 pct Cr was investigated by studying metallographic structure. X-ray line sharpening, electrical resistivity, plastic properties, internal friction, and shear modulus. Appreciable recovery of resistivity, internal friction, and shear modulus together with some hardening and relief of internal strains occurred before the visible growth of a textured substructure above 350°C (recrystallization in situ). The complex behavior of shear modulus, internal friction, and its strain amplitude dependence during annealing are discussed qualitatively in terms of the relative mobility of dislocations. BY plastically deforming fully recrystallized 99.98 pct Cr above the brittle to ductile transition temperature, at -350°C. as in wire drawing, chromium can be made very ductile at room temperature. However, this ductility is lost on annealing at high temperatures when recrystallization takes place.' The present investigation was made to determine the general pattern of the changes in a number of physical and mechanical properties during recovery and recrystallization of heavily deformed chromium as part of an effort to elucidate the reasons for lack of ductility in the fully recrystallized condition. PREPARATION OF MATERIAL Wire specimens 0.027 in. in diam were prepared from arc-melted, electrolytic chromium by extruding, hot swaging and finally wire drawing at 300" to 350°C, i.e. above the brittle-to-ductile transition temperature. The total reduction in area of the wire was 98 pct and the last 3 pct of reduction was made at 100" to 150°C before cooling to room temperature. The impurity content of the material is shown in Table I. Internal friction and modulus measurements were made on a single specimen after annealing in situ at successively higher temperatures. For all other measurements, a fresh specimen was used for each temperature and annealing of these specimens was done in evacuated (0.001 mm Hg) and sealed silica tubes for 1 hr at the various temperatures up to 700°C. EXPERIMENTAL METHODS AND RESULTS The occurrence of a. transition in some physical properties of chromium at - 40°C2 imposed limitations on the temperature region where some of the measurements could be made. The reason for this transition in chromium is at present unknown but is probably associated with an antiferromagnetic state observed below - 40°C.* Heavy deformation produces an anomalous decrease in resistivity when measured at temperatures below -40°C4 though a normal increase is observed above this temperature. On the other hand internal friction in heavily deformed chromium5 over the temperature range 40" to 50°C is invariant with temperature. Above and below this range internal friction is strongly temperature dependent, increasing with increasing temperature. A temperature in this range was therefore convenient for both resistivity and internal friction measurements and for consistency the measurements of the mechanical properties were also made at about this temperature. No structural change has, however, been observed in careful X-ray measurements6 between -195" and 50°C, i.e. departure from cubic symmetry was not greater than 3:10,000; X-ray line sharpening measurements were therefore more conveniently made at room temperature.

Jan 1, 1962

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent papers on interface energies in metals¹,² the concept of an equilibrium of forces has been used in the measurement of interfacial tensions. Mathematically the equilibrium of three forces is given by the relations: where the 2's are the interfacial tensions (interface energies per unit area of interface) of three phases or grains meeting at angles 21 22 and 23 (212 relates to the 1-2 boundary formed by grains 1 and 2;223 to the 2-3 boundary, etc.). If these relationships are valid, one can calculate relative values of the interface energies from measured boundary angles on specimens which have been brought to equilibrium. Since Eq 1 may be derived through a mathematical process of minimizing the grain boundary energy under the restriction that the ?'s be independent of boundary orientation: the concepts of surface tensions and equilibrium of forces are not particularly essential. To deal with the general case involving dependence of boundary energy on boundary orientation, it becomes desirable to drop certain concepts formerly held (namely that energy per unit area is identical with force per unit length or surface tension) and to use the energy concept alone. It is appropriate, therefore, to use E in place of ? in deriving and using the more general equations that express the anisotropic nature of the grain boundary energy. Herring3# ' recently has derived the required general equations using the principle of minimization of energy. Specifying the boundary orientations in terms of angles (4) measured with reference to crystal axes within the grains, Herring's equations take the form E23 + E21 cos?8 + E12 cos?2 — sin ?12 + sin?2-?E12/?12 =O [2] where the partial derivatives are measured in the direction of counterclockwise rotation of the boundaries. Eq 2 implies that an infinitesimal displacement of the triple point along the 2-3 boundary produces no change in the boundary energy. Similar equations apply for infinitesimal displacements along each of the other two boundaries. From such equations Herring obtains the following general relationship (1 + E1 E2) sin?8 + (E2 — E1) cos?3 ________ E38______________ = (1+ E2 E8) sin ?1+ (E3— E2) cos ?1 __________^5____________[3] (1 + E sin ?2, + (E1 — E8,) COS ?2 1 E28 where E1 = 1/E23- E25 and PC and c8 have similar expressions. It is apparent that Eq 3 reduces to Eq 1 when the c's vanish. Eq 3 also reduces to Eq 1 when the E'S are all equal. Shockley and Read' have pointed out one limitation to these equations. When E plotted versus 4 appears as an energy cusp, as their theory requires, for example, for the energy near a twin boundary position, then Eq 3 (and therefore Eq 1 also) no longer applies if one boundary is in the minimum energy position. One of the equations of form Eq 2, however, applies if the infinitesimal displacement is along the boundary associated with the energy cusp. From the foregoing treatment it will be apparent that equilibrium angles alone are not sufficient in general for calculating relative interface energies.

Jan 1, 1951

By M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By J. E. Pavlick, A. G. Guy

The total creep of tin alloys containing antimony in solid solution was observed to decrease with increase in antimony content. However, near the solubility limit an anomalous maximum in deformation was. found, in agreement with similiar observations by Bochvar. IT has long been recognized that alloys may deform more rapidly under stress if there is a tendency for a phase change or other structural change to occur simultaneously. However, the phenomena involved are complex and in some instances the opposite effect, strengthening, may result.&apos; This area of research has not attracted much interest in the western world, and although Russian investigators have studied it for the past 15 years their work has not received due attention here. Recently diametrically opposing views on one aspect of this problem have been espoused by two Russian investigators, Kornilov and Bochvar. The question is this: in certain binary alloys tested in creep at the temperature where the solute is at the limit of solid solubility, does the incipient formation of the second phase strengthen or weaken the alloy? Korni-lov&apos;s arguments in favor of strengthening were presented at the 1954 Symposium at the National Physical Laboratory, =Creep and Fracture of Metals at High Temperatures.The most recent statement of Boch-var&apos;s theory of weakening is in Oding&apos;s new book on creep and rupture.3 Although Bochvar agrees that strengthening occurs in some alloy systems, he argues that in certain alloys an anomalous weakening is observed. However, the extensive work of Korni-lov&apos;s group on creep properties of alloy systems has not revealed any anomaly of this type, but instead has tended to refute Bochvar&apos;s theory. This clear-cut controversy offered a good opportunity for a simple experiment to resolve the problem. The experiment and its results supporting Bochvar are the subject of this paper. However, it will be helpful first to sketch the present status of the larger question of the effect of a phase change or other structural change on plastic deformation. PREVIOUS WORK One of the first researches in this area was by Pfei1,37 who investigated the creep resistance of an 80 Ni-20 Cr alloy containing varying amounts of titanium. He found that the resistance to creep increased rapidly as the solid solubility limit in the alloy at 775&apos;c was approached and slightly exceeded. With further addition of titanium the creep resistance decreased, presumably because of precipitation effects. Bochvar&apos;s first work in this field was a study in 1945 of "superplasticity" in zinc alloys containing 15 to 25 pct Al.4 He found that alloys quenched from about 400 had anomalously low hardness when tested below this temperature. The following year, in a paper on the dependence of mechanical properties on the composition and structure of alloys,5 he extended some observations of Kurnakov to predict that at high temperatures of testing the hardness values for solid-solution alloys might be lower than those for the component metals. He also pointed out the influence of changes in solidus temperature in affecting curves of hardness vs composition, and he

Jan 1, 1962

By R. C. Hassinger, D. V. von Rosenberg

Transverse dispersion has received considerably less treatment in the literature than has longitudinal dispersion. Different methods for determining transverse dispersion coefficients have been used in different investigations, and the results obtained have not been consistent enough to permit accurate generalizations as to the effect of various physical parameters on the magnitude of these coefficients. A numerical solution to the differential equation describing transverse dispersion in the absence of longitudinal dispersion was obtained to enable one to calculate the dispersion coefficient from experimental results. The more general dispersion equation including longitudinal dispersion also was solved numerically to give quantitative limits of a dimensionless group within which the assumption of negligible longitudinal dispersion is justified. Possible experimental procedures were examined, and one utilizing a cylindrical packed column was chosen for the determination of transverse dispersion coefficients. Values of these coefficients were determined for a system of two miscible organic fluids of equal density and viscosity, for two sizes of packing material over a wide range of flow rates in the laminar regime. The dispersion coefficient was found to decrease, for a constant value of the product of packing size and interstitial velocity, as the size of the packing material particles increased. INTRODUCTION Longitudinal dispersion has received extensive treatment in the literature, and consequently is better understood than its orthogonal counterpart, transverse dispersion. Many mathematical models of dispersion processes assume that transverse dispersion is rapid enough to damp out any radial** concentration gradients and therefore may be neglected. Laboratory and production results, however, indicate that this is a poor assumption.l,2 Various experimental procedures for determining transverse dispersion coefficients have been used in previous investigations, but the results have generally been expressed by similar correlations. The transverse dispersion coefficients obtained, however, have often varied considerably for given values of the correlation parameters. We feel that further experimental determinations of transverse dispersion coefficients will help alleviate some of the inconsistencies in these empirical correlations. One assumption implicit in all previous investigations is that of negligible longitudinal dispersion in the experimental system. An attempt to justify this assumption often is made using intuitive reasoning, but it is apparent that this reasoning must break down as the condition of zero flow rate is approached. A mathematical examination of the equations describing the system yields physical limits outside of which the assumption of negligible longitudinal dispersion is invalid. BACKGROUND In a porous medium, the "effective molecular diffusivity" De is less than the molecular diffusivity D measured in the absence of a porous medium, due to the tortuous path which a diffusing molecule must travel. Various authors3-5 have reported values of the ratio De/D in the range of 0.6 to 0.7. When there is fluid flow within the porous medium, mass transfer occurs by convective dispersion as well as by molecular diffusion. These are separate phenomena and can be treated as such on a microscopic scale. However, the mathematical complexity is such that only extremely simple geometries could be considered, and the results hardly would be applicable to the complex geometries existent in actual porous media. A more

Jan 1, 1969

By E. T. Stephenson

Wert and Marx1 pointed out that a straight-line relationship exists between the activation energy of a relaxation process and the temperature at which the maximum relaxation occurs. The data available at the time indicated that this relationship held for a number of Snoek peaks, several grain boundary peaks, and pair relaxation in a brass. Theoretical justification for the observed relationship was found in the following equation, which Wert and Marx derived from the theory of interstitial atomic diffusion coefficients:&apos; where AH is activation energy, R is the gas constant, T is the internal friction peak temperature, v is the interstitial atomic frequency, f is the frequency of the applied stress, S is entropy of activation. More accurate internal-friction data on interstitial diffusion in bcc metals have become available since Wert and Marx&apos;s paper. Table I gives activation energies calculated by several authors from a combination of elastic aftereffect data and the peak temperatures at several frequencies of measurement. (In the case of Fe-C and Fe-N, the referenced authors5&apos;7&apos;8&apos;10 also used high-temperature diffusion data.) However, diffusion experiments at 150°C and above1&apos;-13—rather than anelastic techniques—were used to determine the activation energy of hydrogen diffusion in Fe-H. In order to plot this recent data as a AH vs T graph we calculated the peak temperatures of the systems listed in Table I (with the exception of Fe-C, Fe-N, and Fe-H) by using published values3&apos;&apos; of AH and Do. These calculated peak temperatures varied by only a few degrees from experimentally determined peak temperatures. The calculated values were felt to represent the better average. A number of investigators have found the peak temperatures in Fe-C and Fe-N to be 38 to 40°C and 20° to 24°C, respectively. The values of 39" and 22°C (312° and 295°K in Table I) were determined by carefully executed experiments.6&apos;8 The hydrogen peak temperature has been measured at 1 cps,12 20 cps,14 and 35,000 cps.15 All hydrogen peak temperatures were adjusted to 1 cps for Table I using AH = 3000 cal per mole. As Fig. 1 shows, the data of Table I fit a straight line at least as well as the earlier data used by Wert and Marx. Linear-regression analysis was applied to the data in Table I. The Fe-H data was omitted because the activation energy has not been experimentally determined in the temperature range of the peak. The analysis yields the equation: with a standard error of 860 cal per mole. The agreement of the data in Table I with the Wert-Marx equation is excellent. Strict application of Eq. [I] forces the linear regression analysis through the origin. In this case, the analysis gives a slope of 62.1 cal per mole per deg, and a standard error of *890 cal per mole. With this value, it follows from internal-friction theory that Hence, Do varies by only 30 pct among these bcc-interstitial systems. Thus, a concept suggested originally by Wert and Marx1 is confirmed by recently published data. The

Jan 1, 1965

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique&apos;s possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By John C. Calhoun, J. E. Warren

A study of waterflood efficiency, given in terms of oil recovery at water breakthrough and u1timate recovery, has been made on short, consolidated Pyrex glass cores rendered oil-wet by chemical treatment. Contact angle. interfacial tension, permeability and porosity were the variables considered. Oil and water viscosities, core length and velocity of flooding were held constant. The data permit interfacial tension, contact angle, porosity, and permeability to be grouped into a scaling coefficient along with viscosity, velocity of flooding and length of core. Correlation of the .scaling coefficient with recovery at water breeakthrough is found to follow prediction; correlations of ultimate recovery demand a scaling coefficient different from that which correlates breakthrough recovery. The work indicates that, with proper control, a group of similar natural cores, of permeability plug size, call he correlated 10 indicate basic flooding performance. INTRODUCTION The fraction of oil recovered from a porous medium is related to both reservoir conditions and production techniques. An investigation of all factors that enter into this relationship is necessary in order to arrive at the optimum method of exploitation for oil reservoirs. To define this relationship, laboratory studies have been made by a great many investigators. However. an important obstacle arises if the results of these experiments on water flooding are to be applied to practice. Ditferences in behavior are to be expected between reservoirs of the dimensions encountered underground and those used in laboratory work. Factors which play an important role under laboratory conditions may be of no consequence in reservoirs. Laboratory operating practices generally differ from field operating practices. Thus. a mere understanding of the mechanism of the displacement of oil by water is not enough. It is just as necessary that the process be analyzed dimensionally to give continuity and validity to the conversion from laboratory to field. The theory of oil displacement that has come to be accepted by the majority of those who are associated with reservoir mechanics had its beginning in the work of Leverett¹ and Buckley and Leverett2. The banking of oil, observed by many previous workers, was described by the "fractional flow" and the "frontal advance&apos;&apos; equations. The validity of the Buckley-Leverett theory was substantiated by the experimental and theoretical work of Terwilliger et al³; moroever, the theory was extended by the introduction of the idea of a "stabilized zone" to describe the banking of oil. Levine5 showed that the Buckley-Leverett equations gave reasonable agreement between calculated and experimental breakthrough recoveries only if the capillary pressure and gravity terms were included. Rapoport and Leas1 investigated the properties of linear floods and showed that both breakthrough and maximum recovery are related to a "scaling coefficient&apos;&apos; derived from the Buckley-Leverctt equations. Jones-Par-ra and Calhoun6 presented another scaling coefficient which included both viscous and capillary variables. Such scaling coefficients should suffice to predicl waterflood efficiency. However, some experimenters report data which does not appear consistent with the healing coefficient approach. For example, Engelberts and Klinkenberg7 conducted an extensive series of experiments on a dimensional model which contained a

Jan 1, 1956

By Oscar Weiss

An aerial magnetometer survey was carried out by the author&apos;s geophysical organization over the Vrede-fort dome, where Witwatersrand beds are wrapped around a granite plug 25 to 30 miles in diameter. The well-known magnetic shales of the Lower Witwatersrand system (to be referred to as LWW) give strong negative anomalies over the out-cropping portion of the dome. This is unusual as these same shales cause positive anomalies over large areas near Johannesburg and along a strike of 130 miles between the East Rand and Klerksdorp. It is suggested that the negative polarization is caused by heat and stresses connected with the doming. This negative polarization of sedimentary beds, which usually cause positive anomalies, is a good example of how "magnetic lows" can be caused by "structural highs." Significant magnetic anomalies should be tested by gravity and seismic methods irrespective of the sign of the anomalies. South of the line X — Y (see Fig 2 and 5) the gravity anomalies are smaller over the LWW beds and magnetic anomalies suddenly become weaker and even change signs by becoming positive. This peculiar phe- nomenon is explained by faulting which truncated the nearly vertical LWW shales at depth. In this manner the mass of the LWW beds has been reduced together with the weakening of the negative magnetic anomalies by positive poles which occupy the truncated end. Furthermore, by uplifting the beds between f1 and f2 (Fig 2) positive polarization becomes predominant, thus causing positive magnetic anomalies. General The Vredefort dome is one of the internationally known geological structures, which, among others, has attracted the attention of numerous American geologists. It was for this latter reason that our aerial magnetic results over this structure were selected by us for publication in the United States of America. A full description of the exposed geology has been published by Nell and readers are referred to this paper, which is subject to only slight modifications inasmuch as the subdivision of the Witwatersrand system (to be referred to as WW system) is concerned. The Vredefort dome is about 60 miles southwest of Johannesburg. The WW system, after being exposed in the vicinity of Johannesburg, plunges with southerly dips beneath the Vent-ersdorp and Transvaal systems. Along a section southwest from Johannesburg, as shown diagrammatically in Fig 4, we see no outcrops of the WW system until the Vredefort dome, where the Upper and Lower WW system are wrapped around an almost circular arc of a granite mass. Here the whole WW system is overturned around the perimeter of a huge granite plug 25 to 30 miles in diameter. Less than half of the circumference of this dome is exposed; the rest is covered by Karroo dolerites and sediments. The determination of the exact shape of the concealed part of the dome has been a matter of considerable interest and obviously geophysical methods were eminently suited for obtaining this information. A good start was made with a gravimeter survey carried out by the Geological Survey of the Union of South Africa.2 Our own

Jan 1, 1950

By James H. Boettcher

INTRODUCTION There are many and varied sources of finance available to the mining industry for exploration, development and/or the operation of mining projects and companies. These sources include equity from major as well as "penny" stock exchanges, precious metal mutual funds, private investor groups (from "grubstakes" to tax-oriented limited partnerships) and banks. The variety is representative of the fact that the world&apos;s capital markets are segmented and stratified according to risk-reward characteristics. This interrelationship is summarized in Exhibit I and 2 which relate (very approximately) various sources of finance to a typical mining project&apos;s life cycle and risk-return characteristics. The objective of this paper is to introduce, as it applies to the mining industry, a somewhat recent phenomenon represented by one of these capital markets segments referred to as "venture capital." Venture capital investing per se, which today is a multibillion dollars per annum investment business, goes back as far as Queen Isabela&apos;s backing of Columbus&apos; "wild ideas." The real institutionalization of the venture capital process really began in earnest, however, after World War II. Today over 700 private venture capital sources (and more government related ones) exist providing funding to a range of industries, but typically related to the "high-tech" business. The table to the right shows industries financed by venture capital funds between 1980 and 1982. Conspicuous by its absence is, of course, mining which is not a great surprise since typical mining projects up until recently were large, required long lead times and were undertaken by established mining houses. Also, as most of you can appreciate, successful investing in the mining business requires a great deal of experience and understanding of the industry which most venture capital funds do not have. TARGETED RETURN The rate of return objective of most venture capital funds is, according to the legalized version, to realize a return which is "substantially in excess of that obtainable through conventional equity investments." One may say that a common objective of venture capital funds is to realize a 20% to 30% compound annual internal rate of return on capital over their life which is often ten years. [ ] This objective has been recently more feasible in the mining sector due to the development of smaller precious metal projects which cost less and are quicker to generate cash flow than the behemoth projects of the 1970s. In addition to precious metals, venture capitalists have invested or looked at a variety of other mining projects including ones as prosaic as a high margin "kitty litter" operation, sand-gravel and other industrial minerals operations, the leveraged buyouts of coal mines or mineral divisions of major energy or mining corporations, and even in in-situ copper or gold leaching ventures. A typical investment is in the range of $100,000 to $3,000,000 although some can go as high as 5,000,000. This implies a project size up to, say, 30,000,000 if a venture capital fund does it on its own. Larger projects can be done if the equity portion of the investment is syndicated with other investors.

Jan 1, 1985

By M. C. Leverett, S. E. Buckley

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.&apos; and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult&apos;s law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry&apos;s law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry&apos;s law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By J. H. Scaff, H. C. Theuerer

Germanium may be reversibly converted from n to p type by heat treatment. Data for the conversion and the associated changes in resistreatment.tivity are given and the results are interpreted in terms of changes in the donor-acceptor balance. MEANS for controlling the electrical properties of germanium in a predictable manner are of interest because of the increasing utilization of this element as the semiconducting material in electrical devices. Since both the mechanism and the magnitude of the electrical conductivity depend upon the kind and quantity of impurities present, the conductivity usually is adjusted by first carefully purifying the germanium, and then, by standard alloying procedures, adding the elements desired. The elements usually added are from the third or fifth periodic groups depending upon whether p- or n-type germanium is desired. However, in the development of germanium rectifiers during the war, it was found that it was possible also to modify reversibly the conductivity of germanium and even to produce conversion from n to p type by heat treatment.1,5 Since then a detailed study of this effect has been made. The data are presented in this paper and an explanation is offered for the effects observed. Preparation and Experimental Procedure The method used in preparing the germanium ingots for this investigation has been previously described.&apos; The method consists essentially of (1) reduction of GeO2* and (2) preparation of a 50-g ingot from the reduced material. Graphite containers are used in both steps. In the first step the GeO2 is reduced in hydrogen at 650 °C to form a sponge germanium which, to assure complete reduction and to obtain massive materials, is fused subsequently in the reduction furnace by gradually raising the temperature to 1000°C. The button of germanium thus obtained corresponds to a yield of 99.8 pct. The final ingot is prepared by fusion of the germanium button in a helium atmosphere. A cylindrical crucible in a vertical silica tube furnace is employed and the crucible is heated by an external induction coil. The ingot is solidified from the bottom upward by raising the induction coil at a constant rate with power to the coil kept at a fixed value. In such ingots, segregation is normal and most of the impurities are concentrated in the last region of the ingot to freeze. It follows then that the major portion of the ingot is purer than it would have been if freezing had occurred in a random fashion. Moreover the orderly advance of the freezing surface during solidification establishes in the ingot a succession of surfaces of constant composition, if it is assumed that the liquid is homogeneous and that diffusion in the solid is negligible. Therefore, some information on the distribution of impurities in the ingot may be acquired by determining the shape of the solid-liquid interface at different stages of solidification. This is of importance because the concentration of impurities will be seen to affect the response of germanium to heat treatment. Such information is difficult to acquire by direct means, for the impurities responsible for the electrical properties of germanium prepared in this way are present

Jan 1, 1952

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas&apos; have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968

By S. E. Buckley, M. C. Leverett

THE production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. INTRODUCTION Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,1 and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. ROLE OF DISSOLVED GAS When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1941

By S. E. Buckley, M. C. Leverett

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By B. Fazan, O. D. Sherby, J. E. Dorn

McLean&apos;s technique was employed to determine the effect of temperature on the contribution of grain boundary shearing to the total creep strain in pure aluminum over the range of 610° to 747°K. The contribution of grain boundary shearing at the same stress was found to depend upon a temperature-compensated time, where the activation energy AH was practically identical with that for total high temperature creep. SEVERAL outstanding investigations by McLeanl-&apos; have demonstrated that the total creep strain in polycrystalline aluminum at 473°K arises from microscopically detectable slip, subgrain tilting, and grain boundary shearing. Whereas microscopically detectable slip arises from dislocations that move out of the grains, subgrain tilting is due to entrapment of dislocations of like sign in subgrain bound-arles. Consequently, creep in polycrystalline aggregates appears to be the resultant of two mechanisms, namely, migration of dislocations and grain boundary shearing. This suggests that an appropriate law for creep should contain two additive terms ?1 = ?d + ?yb where the total creep strain, ?1, depends on the sums of the creep strains arising from motion of dislocations, ?d, and from grain boundary shearing, ?yb. But extensive investigations5 over wide ranges of alloys, grain sizes, temperatures, and stresses have shown that the total creep strain is quite accurately dependent on the single term functional relationship ?1 = f (?), s = constant where s is the stress (constant),* ? = te-?H/RT, t is the time under stress, AH is the activation energy, R is gas constant, and T is absolute temperature. Since Eq. 2 was found to be valid over those ranges where appreciable grain boundary shearing is observed, it appears probable that the activation energy for grain boundary shearing might be identical with the activation energy for migration of dislocations. Thus, under a given stress, it could be thought that where fd and fgb represent the appropriate functions for each mechanism of creep. The primary objective of this investigation was to obtain a direct check on the accuracy of this hypothesis. Experimental Procedure and Results Rolled aluminum sheet (99.987 pct Al), 0.100 in. thick, was used in this investigation. Creep specimens having a 0.25 in. wide, 3 in. long gage section were so machined that their axes were in the rolling direction. All specimens were annealed for 9 hr at 894°K before testing to produce a mean grain diameter of about 0.1 in. One face of each specimen was polished electrolytically in 10 pct HBF4. In order to permit accurate measurements of grain boundary shearing, the polished surface was lightly scribed with a ruling machine accurate to ±0.0001 in. to give a uniform grid of lines which were 0.01 in. apart. Although it was thought that surface working might modify the creep behavior in the vicinity of the scribed grid lines, this technique nonetheless was employed because such local differences in creep properties should not modify seriously the fractions of the total creep strain due to grain boundary shearing or to migration of dislocations. All creep tests were conducted under constant load with an initial stress of 250 psi. The specimen tem-

Jan 1, 1955

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.&apos; The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith&apos; indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.&apos;&apos; Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By R. A. Deju, R. B. Bhappu

Further information on the surface characteristics of the silicate minerals was obtained by experimentally correlating the oxygen-silicon ratio of the silicates with their electrokinetic properties. Specifically, the behavior of the minerals in an electric field was investigated using zero point of charge as a parameter. A modified electrophoresis cell was used for the determination of electrophoretic mobilities. It was shown that there is an increase in the zero point of charge with increasing oxygen-silicon ratio in the silicates. Finally, a chemical interpretation was presented to describe the surface phenomena observed in the experiments. In recent years great interest in surface chemistry has produced a number of methods to study the surfaces of minerals and to observe the phenomena occurring at their interfaces. One such method is discussed in this paper. A rather complete review of the surface characteristics of the oxide minerals has been undertaken by parks,&apos; but, a similar study has not been made for the silicate minerals. Two previous papers by the authors2&apos;3 attempted to remedy this situation. In these papers it was demonstrated that the reaction between the silicate mineral particles and acidic water involves mainly an exchange of metal ions for hydrogen ions on the surface of the solid, leading to an increase in pH of the aqueous phase. Also, the degree of reaction was found to depend on the oxygen-silicon ratio of the silicate structure, being least for the quartz and greatest for the olivines. A hypothesis was then set forth explaining that upon the fracturing of a silicate mineral, the oxygen-metal bond (which is almost entirely ionic in character) will break more easily than the stronger oxygen-silicon bond. This results in the exposure of unsatisfied oxygen sites on one hand and active, exchangeable cations on the other. These active sites on the fractured surfaces are then available for reaction with the hydrogen ions in acidified aqueous solution. Thus, an increase in degree of adsorption of hydrogen ions occurs as the oxygen-silicon ratio increases due to the presence of a larger number of active sites on such minerals. A correlation between oxygen-silicon ratio and electrokinetic properties will be further pursued in this paper from both the theoretical and experimental points of view. Efforts will then be made to present a chemical interpretation of surface phenomena observed in the experiments. It is believed that this study may supply pertinent information on the behavior of silicate minerals in froth flotation systems. ELECTROKINETIC STUDIES Equipment: In a previous paper,2 Deju and Bhappu described a simple method for determing the zero point of charge using a potential across a cata-phoresis cell and observing particle movement by means of a Rayoscope* optical system. This setup is simple in design and operation and extremely reliable. With care, reproducible results within 1.5% accuracy may be obtained. A new setup has been developed, based partly on the design by Zeta-Meter Corp.4 and partly on previous cells used at the New Mexico Bureau of Mines. This new, modified cell is shown in Fig. 1. Although

Jan 1, 1967