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By J. M. W. Mackenzie, M. H. Buckenam

Flotation experiments using stearic, oleic, linoleic, linolenic, and ricinoleic acids and naturally occuring products rich in these acids as collectors for calcite are described. The results confirm the validity of the rule of Hukki and Vartiainen relating the collecting power and unsaturation of the C18 acids. Reasons for this relationship are discussed and a close relationship between mineral depression and critical micelle concentration is reported. It has long been recognized that the unsaturated fatty acids are in general superior flotation collectors to their saturated homologues. Whereas earlier workers concentrated on saturated and monoethe-noid acids, recent investigations have centered on oleic, linoleic, linolenic, and the substituted mono-ethenoid acid: ricinoleic. From studies of the collecting properties of palmitic, oleic, linoleic, and linolenic acids on ilmenite, rutile, hematite, and magnetite, Hukki and Vartiai-nenl concluded that the collecting power of fatty acids increased with unsaturation of the hydrocarbon chain. Sun, Snow, and Purcel12 investigated the collecting properties of unsaturated fatty acids as collectors for phosphate ores and concluded that the collecting power increased with increasing unsaturation of the hydrocarbon chain up to two double bonds and that further unsaturation decreased the collecting power. More recently Sun3 studied the collecting power of the C18 fatty acids stearic, oleic, linoleic, and linolenic on 37 minerals. The results of these experiments with a few exceptions showed that the collecting power of the acids increased in the order stearic, oleic, linoleic, and linolenic. The relative collecting powers of linoleic and linolenic acids were in many cases altered by the cleanliness of the mineral surface prior to flotation. Sun concluded that linolenic acid may become oxidized by atmospheric oxygen during flotation, a reaction which would reduce its effectiveness as a collector. This deduction is supported by Gaudin and Cole4 who concluded that oleic and linoleic acids do not undergo appreciable oxidation of the double bonds during flotation but that the linolenic acid double bonds are measurably affected. The most complete investigation on the influence of hydrocarbon chain unsaturation on the collecting properties of fatty acids is that of Kivalo and Lehm~svaara.~ These workers using linolenic acid of a higher purity than Hukki and Vartiainen showed that this acid was superior to oleic and linoleic acids as a collector for magnetite. They also found that ricinoleic acid was a more effective collector for this mineral than the other acids investigated, an observation particularly apparent at high collector concentrations. Seeking to explain the superiority of the unsaturated acids these authors considered the effects of critical micelle concentration, surface activity, hydrolysis, and cross sectional area of the hydrocarbon chain in relation to unsaturation. Using what, according to the results of Caviere are erroneous surface tensions of the soap solutions of these acids, they concluded that the surface activity decreases and the critical micelle concentration increases with increasing unsaturation. In view of the data of Cavier, whose results show that surface activity of these soaps increases with unsaturation, the deductions of Kivalo and Lehmusvaara are open to criticism. The degree of hydrolysis of the soap solutions as measured by Kivalo and Lehmusvaara decreases as the unsaturation of the fatty acid increases, a result which helps to explain the superiority of unsaturated acids as collectors. In view of the superiority of unsaturated acids as collectors for many minerals, attention has been directed towards the utilization of fatty acid raw materials such as tall oils and linseed oils which contain considerable quantities of these acids. This paper describes test work to determine the effect of unsaturation of the hydrocarbon chain on the collecting properties of fatty acids on calcite, and includes comparable test work using natural products rich in unsaturated acids. TEST WORK Reagents: The pure fatty acids used were oleic, linoleic, and linolenic. Of these, oleic was supplied by British Drug Houses Ltd. and the others were produced by the Hormel Inst. When not in use these

Jan 1, 1961

By J. A. Church

I. Early Furnaces,......423 11. Experiments with the HIgh-Shaft FURnace,..... 426 III. ExperMents wIth the Wide FURnace,..429 IV. ExperEentS with Extreme BOSH,... 43.2 V. Survival of the 56 by 180 IN. Furnace,.434 VI. Recent ExpeEiments,.....436 VII. SUMMary,........438 I. Early Furnaces. Copper blast-furnace construction in America has long recognized a general standard in the rectangular water-jacketed shaft with separate forehearth. The details, however, and especially those relating to shaft dimensions, have had to meet a great variety of conditions, and show no uniformity whatever. Selecting a few of the present day Western plants, we find furnace lengths varying from 12.5 to 87 ft., widths at tuyere level from 42 to 84 in., and heights above tuyeres from 5 ft. 4 in. to 22 ft. 4 in.; and comparing present designs with those of the past, we meet contrasts no less striking. Unlike its transverse section, the length of a furnace has come to depend rather on the size of unit desired than on the requirements of smelting; and if the question of length be ignored, several of the various existing designs can be grouped together on the basis of a common transverse section. This section, having a width at tuyere level of 56 in. and a height above tuyeres of 18 ft., was developed at Great Falls, and the story of its development contains some interesting features. Ground was broken for the Great Falls works in the spring of 1891. About a year later, the concentrator was able to begin operation, followed within the next few months by the Brueckner, reverberatory, and converter departments, and in April, 1893, by the first blast fur-

Jan 1, 1914

By G. W. Tracy, R. D. Carter

Numerical calculations were made to determine the behavior of reservoirs with high-pressure drawdown and wide well spacing where the initial productivity is low and the wells are completed by hydraulic fracturing. The two-phase flow equations were solved for the flow into a single well. This well was assumed to be producing from a reservoir with hydraulically created horizontal fractures (four different systems with fractures were studied). For comparison purposes, additional two-phase flow calculations were made assuming a reservoir with uniform rock properties. The two-phase flow results were also compared with the conventional calculation methods, which do not include the effect of saturation gradients resulting from a simultaneous flow of oil and gas which are normal to this type reservoir. It was found that the conventional methods predict (1) a high and too optimistic value of ultimate recovery, (2) a high producing rate and a high reservoir pressure at a given oil recovery and (3) a low trend of gas-oil ratio with oil recovery. Included in the two-phase flow calculations were provisions to control the oil production rate by an allowable rate and, also, by a gas-oil ratio penalty rule. For the systems with hydraulic fractures, the producing rate was controlled by the gas-oil ratio penalty rule for most of the life. This is in contrast to the system with uniform rock properties which went "on decline" almost immediately. An unexpected characteristic of the systems which included fractures was the early rise in producing gas-oil ratio from 730 cu ft/bbl to approximately 1,200 cu ft/bbl, followed by a "leveling off" before the normally expected gas-oil ratio rise began. Additional features which are a result of hydraulic fracturing are (I) greater ultimate recovery, (2) higher average producing rates and (3) a lower average reservoir pressure at a given oil recovery. INTRODUCTION Some oil fields discovered during the past few years are producing from certain volumetric ally controlled reservoirs (often referred to as solution or internal gas- drive reservoirs) which are characterized by high-pressure drawdown at the wells. Since the available pressure drawdown at a well is limited by the static reservoir pressure and the producing rate is controlled by the available drawdown, wells completed in this type of reservoir usually produce at a rate less than the allowable from the time of completion. Because of this, this type of reservoir is referred to as a low productivity reservoir. Economic considerations require the use of wide well spacing and well stimulation by hydraulic fracturing to make commercial wells in this type of reservoir. Performance predictions for volumetrically controlled reservoirs have been made using a combination of two standard equations. 1. The "Schilthuis" or "Muskat" type material balance equation is used to relate the average reservoir pressure and the cumulative oil recovery. 2. The results from the material balance equation and the productivity factor as described by Pirson' are used to relate the cumulative recovery with producing rate and time. The material balance equation assumed uniform pressure and liquid saturation conditions throughout a reservoir. The steady-state radial flow formula allows for a pressure gradient toward a well but assumes uniform liquid saturation. These calculation methods are adequate for application to reservoirs wherein the drawdown at the well to realize satisfactory producing rates is small compared to the total pressure. In low productivity, volumetrically controlled reservoirs, the pressure drawdown at the well is large cornpared to the total pressure. Although a precise number cannot be given for the magnitude of a large pressure drawdown, values in excess of 1,000 psi would definitely be included. For practical considerations, this usually occurs when the formation flow capacity is less than about 100 md-ft. However, this limit of formation flow capacity will vary with the well producing rate. The low pressure in the neighborhood of the well which results from a high drawdown causes evolution of large volumes of gas. This causes the gas saturation to be higher near the well than at a greater distance—-hence, a non-uniform gas saturation. Also, the relationship between the relative permeability to oil (K/K) and gas saturation is nonlinear but decreases approximately in an exponential way with increases in gas saturation. Because of this, the following chain reaction is established.

By Thomas C. Wilder

The activities of both components and the partial and integral molar thermodynamic properties of mixing for the liquid Al-Ge system at 1200°K and for the gertnanium-rich Al-Ge liquidus have been determined from data for eighteen alloys of compositions in the range 0.0593 < 0.880 using the reuersible gal-vanic. cell in the temperature interval 9320 to 1258°K. The liqui-dus compositions above 93 2 °K loere also ve determined by observing the discontinuities in the C us T plots for the high-melting alloys. This system shows moderate negative deviation from ideality throughout, the values for y° being 0.212 and 0.189 for aluminum and germanium, respectively, at 1200°K. Pavtial molar Properties of aluminum on the germanium-rich solidus and at infinite dilution in Ge(s) oboue 932°K were estimated from the foregozng measurements and the equlibrium data of previous investzgators. RECENT compilations of data1" have shown an increasing demand for knowledge of the thermodynamic properties of mixing of metallic alloy systems. In the case of binary-liquid systems where one of the components is a semiconductor this information is useful because, primarily, properties of the second (dopant) component on the liquidus, solidus, and at infinite dilution may be determined more accurately than from calculations based on the phase diagram. In this investigation a reversible galvanic cell was used to determine the chemical potential of aluminum in the two-phase region, liquid + [Ge], on the germanium-rich side of the A1-Ge system in the temperature range 932" to 1193°K. In addition, similar measurements for homogeneous liquid A1-Ge alloys for the entire composition range were obtained for the temperature interval 932" to 1258°K. The cell used was: The experimental technique and the treatment of the data were essentially the same as described earlier394 and are elaborated upon only briefly here. Each cell consisted of a liquid aluminum anode and three A1-Ge alloy cathodes of different composition which were held in Morganite alumina crucibles. The alloys were made up from aluminum and germanium weighed to the nearest 0.1 mg to a total weight of 5 to 10 g. Aluminum was a gift of Aluminum Co. of America and had a purity of 99.995+ pct. Germanium of transistor grade was a gift of Bell Telephone Laboratories. The four electrodes were contained in a larger alumina crucible which also held the prepurified fused chloride electrolyte. Contact to the electrodes was made by tantalum wire leads sheathed in alumina. The tantalum leads were centered in the electrodes by suitable positioning of an alumina radiation shield which fitted on the top of the - alulnina crucible. Two chrome l-alumel thermocouples, sheathed in quartz wells, completed the internal cell arrangement. The entire assembly was enclosed in an alumina tube, fitted with a water-cooled copper head so the system could be evacuated and then flushed with purified argon. *

Jan 1, 1967

By P. Barnes

The subdivisions of this account are numbered 27, 28, 29, 30, 31, 32, and 33, in the general series of construction accounts, and give the details of cost of the various items of the work, as noted below: Accounts 32 and 33 relate to hand-tools and to heaters, and, being quite small in total amount, are omitted in this statement.

Jan 1, 1879

By E. S. Bumps, W. F. Craig, M. Baeyertz

Metallurgists have looked at fractures macroscopically for many years and have evolved a vocabulary in which such words as "cleavage," "brittle," "shear," "ductile," "granular," "fibrous," and "silky" are used to describe the appearance of the fractured surface; but the meaning of these words in terms of metal structure is not well established. Observations of the structural meaning of "brittle" and "ductile" fractures in plate steels have been made, notably, by Kramer and coworkers1 and by Tipper.2 Grossman3 has studied the fracture of tempered martensite and combinations of ferrite and martensite. Notwithstanding these and other less concerted attacks on the problem, present understanding of fracture rests more on assumptions and logic than on experiment. It is the purpose of this paper to add a little to the growing fund of experimental observations of the nature of fractures in steel. The particular fractures to be described were obtained in conventional impact testing of an ordinary structural steel shape. In impact tests of the Charpy type, the specimens fail in a characteristic manner that depends on the steel and the temperature of testing. With ordinary structural and many other steel products, an appropriate range of testing temperature will cause a considerable change in the energy absorbed before fracture. This change is known as the energy transition and is accompanied, more or less closely, by alteration in the appearance of the fracture. At testing temperatures below the transition, the terms "brittle," "cleavage," or "granular" are used to describe the fracture; above it, "ductile" or "shear" are often used. Within the transition, the fracture changes from "brittle" to "ductile" by a progression in appearance, wherein the "brittle" portion of the fracture becomes restricted to a smaller and smaller central area of the fracture, as the testing temperature is raised and the "ductile" type of fracture is approached. All this is well known to metallurgists. The specimens under consideration are of the conventional V-notch Charpy type. They were taken from a structural steel shape of the following analysis: C Mn P S Si 0.17 0.46 0.009 0.029 0.03 Both longitudinal and transverse specimens were tested and examined. Fig 1 shows the energy values plotted against testing temperatures in the usual way. The curves for both longitudinal and transverse specimens show an energy transition, although the maximum energy absorbed at testing temperatures above the transition is greater in the case of the longitudinal specimens. Fig 2 illustrates the changes in the macroscopic appearance of the fractures that are associated with the energy transitions shown in Fig 1. Macrographs of the fractured surfaces of the specimens have been identified with the fracture ratings at intervals on each fracture curve. The numerical fracture rating on the ordinate of Fig 2 indicates the percentage of the area of each fracture that was considered to be "brittle" on macroscopic observation. Such rating of the fracture type in impact tests is now customary in many laboratories. Hereafter the specimens will be identified by reference to Fig 2 as 90 pct "brittle," 80 pct "brittle," and so on, in accordance with this macroscopic evaluation of the appearance of the fractured surface. The discussion of the fractures is divided into three parts. The first two are concerned with the mode of fracture and its relation to general structural features. As the same metal-lographic features occur in both longi-

Jan 1, 1950

By D. T. MacRoberts

This paper embodies the results of theoretical studies concerning gas reservoirs, especially the effect of drilling programs of various intensities upon pressure depletion and ultimate recoveries. The primary objective has been to determine the net quantity of recoverable gas that could be obtained as a result of each additional well, in comparison with the gas . that might be secured from a single well ideally placed with respect to both acreage and geological structure. No method is yet known whereby the relative merits of intensive and sparse drilling can be compared experimentally; a reservoir must either be drilled closely or developed with wide spacing, but both programs cannot be conducted simultaneously. Hence, the analytical method seems to be the only approach to the problem. While the present state of our theoretical knowledge does not offer a precise solution to the problem of gas flow in sand bodies, it takes such appropriate cognizance of the limitations of the methods used as to restrict any answer obtained to the realm of engineering accuracy. In solving the problem for the average gas field, it was found that practically the same answers resulted as to pressure distribution, regardless of the size of the drainage radius, even though the latter was assumed to vary from a few feet as a minimum to that of the entire reservoir as a maximum. Such limits represent extreme possibilities; therefore, the practical conditions that are associated with normal development programs, in which wells are placed in the center of tracts varying in size from 40 to 640 acres, will of necessity result in less extreme variations than those indicated in the tables accompanying this paper. Stated more concisely, the amount of gas unrecovered at abandonment (of the particular field used for illustrative purposes) will lie somewhere between 4.6 and 6 per cent of the total original content, no matter how intensively the field is drilled. Gas reservoirs may be divided into two general types, those in which the energy is intrinsic, and those of which the energy is extrinsic. † The first type contains energy in the form of a compressed gas, which expands

Jan 1, 1938

By C. H. Brehaut, W. N. Taylor, R. S. Douglas, H. A. Shannon

THE name for this new method of mining is derived from a composition of Horizontal, Radial, Diamond, and the drilling is from raises. This method, worked out at Copper Mountain, B.C., is believed to be distinct in many features from other known methods. GEOLOGY The ore deposits of Copper Mountain are related to the Copper Mountain stock, which is an ideal example of the magmatic differentiation in that it grades from a basic gabbro at the border to an almost pure orthoclase-pegmatite core. The "contact" ore bodies lie along the contact of the gabbro and an older complex of volcanics and sediment termed the "Wolfe Creek" formation. These older rocks, collectively referred to as greenstone, had been fractured prior to the intrusion of the stock and were highly metamorphosed during the intrusion. The "outlying" ore bodies are somewhat different in character, though a similar structural pattern prevails. It is believed that a deep-seated magma of which the Copper Mountain stock is a part has given off solutions that caused a partial granitization of some of the volcanics. Mining problems are caused further by the presence of a series of soft barren dikes intersecting a great many of the ore bodies, which are about 30 ft. wide, strike north-south, and dip at a high angle to the east; and are further increased by the presence of four major faults, with a great many minor faults running at acute angles from them. Fault zones average 8 ft. in width, and consist of gouge and breccia. They strike northeast and dip steeply to the northwest. The faults cut through the ore zones and the dikes, and continue on into the gabbro. The general mine structure with two types of ore bodies, bounded by weak walls and intersected by several series of soft barren dikes and major faults, indicated that a method of mining should be devised that would remove the ore at low cost with the least disturbance of the waste walls and dikes. THEORETICAL ESTIMATE OF STOPING WITH THE DIAMOND DRILL After consideration of various methods, the most suitable one appeared to be horizontal drilling to break the ore in a manner similar to shrinkage stoping. Drilling vertical holes or rings from a bench and breaking to an open slot was eliminated because the weak walls of ore, dike or waste would not permit this type of opening. It was then decided to drill either horizontal radial holes from a raise or parallel holes from a slot cut across the ore body. After discussion, the latter method was believed unsuitable, for the following reasons:

Jan 1, 1945

By Zay Jeffries

TUNGSTEN has the highest melting point of all the known metals, namely 3350° C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely. brittle and fragile at room temperature, and when possessing a fibrous structure it maybe ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and. ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given.

Jan 6, 1918

By J. J. Pye, J. B. Drew

The surface-diffusion coefficients of Ni63 diffusing on low-index planes of nickel single crystals have been measured over the temperature range from 400° to 1000°C using a precision autoradio-gvaphic technique. The activation energy for sur -face diffusion appears to he the same on the {111}, {110), and (100) planes and amounts to -0.60 ev. This is in good agreement with the value (-0.62 ev) reported for (111) planes obtained by mass-transport techniques. In an earlier paper, the authors have reported self surface-diffusion coefficients on silver.&apos; In that work, a deviation of the diffusion coefficients from linearity in the Arrhenius plot was observed at high temperatures. This effect was attributed to a loss of tracer atoms into the bulk by volume diffusion. The purpose of the present work was to extend the technique developed to the nickel surface-diffusion system up to the point where volume diffusion would come into play. The nickel system especially lends itself to this technique due to the high efficiency of the isotope in darkening the film and the large absorption of the weak radiation (0.063 mev /3- particle of the trapped tracer atoms. The diffusion coefficients and ictivation energy for different orientations on nickel can also be compared with a report published by Blakely and Mykura 2 where a mass-transfer technique was used. This paper reports the self surface diffusion of nickel on the low-index planes over a wide temperature range using a precision autoradiographic technique. EXPERIMENTAL PROCEDURE The experiment is similar to that described in the earlier publication consisting of a radioactive needle as a source resting on a flat, smooth, chemically polished surface annealed in a dynamic dry-hydrogen atmosphere. The needle is held snugly on the surface by a holder fabricated from commercially pure nickel. The point source is made by grinding down a small-diameter nickel rod until a tip of approximately 0.1 mm radius is formed. It is then etched and the needle tip plated with the radioactive isotope Ni63. Nickel single crystals were used whose main impurities were spectrographically determined as Co 0.05, Fe 0.007, C 0.005, and S 0.003 pct. The surfaces, oriented to within 1/2 deg of the low-index planes, were carefully mechanically polished and etched in a 50-30-10-10 hot solution of acetic, nitric, sulfuric, and phosphoric acids giving a smooth polished surface. The crystals were then washed in distilled water and alcohol. Annealing temperatures ranged from 400° to 1000°C with a furnace arrangement in which the crystals could be brought up to temperature in times short compared to diffusing times. The temperature was maintained constant to ±10°C. In the temperature range investigated, the ratio of the surface-diffusion coefficient to the volume-diffusion coefficient (Ds/Du) was 105 or more and the mean bulk-penetration values, calculated from literature values of volume-diffusion coefficients,3 were on the order of 10-5 cm. After the diffusion anneal, the sintered needle is removed, and both the radius of the needle point and spot left on the crystal face are measured. The crystal is then placed on photographic film. Diffusion profiles are obtained by scanning the film with a recording microdensitometer which has a slit width of 10µ. DISCUSSION AND RESULTS The experimental conditions are such that the source strength and needle radius are essentially constant and the time is adjusted such that the mean bulk penetration is small. An exactly analogous heat-flow problem has been considered by Carslaw and Jaeger4 and the solution can be written in integral form as:

Jan 1, 1964

A LARGE attendance at the annual dinner of the Institute, to be held this year on Tuesday eve-ning of convention week, is already assured. Presentation of the Douglas, Hunt and Saunders medals will attract unusual attention since not only in Blaylock, Mathews and Hoover the Institute will be honoring men who have made notable contributions to the advance-ment of their profession, but as to one of them each person as he passes down the reception line will be won-dering whether in renewing acquaintance with our past-president and present Secretary of Commerce, he is not greeting the next president of the United States. Elsewhere in this issue accounts of the professional careers of these three men appear as also of the two younger men, Charles H. Herty, Jr., and P. H. Royster, who are to receive the Robert W. Hunt and the J. E. Johnson awards. Institute honors go for technical achievement, but the Institute will be proud and happy if the nation should later confirm its own judgment by placing larger responsibilities on one of its members. The medals are to be presented at the annual dinner following the President&apos;s reception and preceding the dance. There will be no. other speeches and since the occasion falls on Carnival Night a particularly gay evening is anticipated. The event will be at the Wal-dorf as usual, and members are urged to return prompt-ly the reservation cards sent them by mail. Other entertainment features will include a Smoker, Monday evening at 8.15, held at Mecca Temple and in charge of a new committee with Fred Kay of the Petro-leum Division as chairman. He promises that vocal music will not be allowed to interrupt conversation. Lunch will be served each day on the Fifth Floor of the Engineering Societies Building, and ten special luncheons and dinners have been arranged for particu-lar committees and groups as shown by the detailed program. The Woman&apos;s Auxiliary has laid out a gen-erous program including luncheons, teas, a theater party on the night the men folks go to the Smoker, visits to museums and, not the least important, a round of the leading shops. The Excursion Committee is arranging for an excur-sion sure to be of interest. The American Smelting and Refining Co. has opened its great Perth Amboy plant to the Institute, and on Thursday, Feb. 23, a party will be taken to it by bus traveling through the Holland Tunnel en route. Full opportunity will be afforded those interested to see the workings of the ventilation system of that great public work. If a sufficient number indicate interest, arrangements will be made for group excursions to other plants in the vicinity of the city.

Jan 2, 1928

By Bernard Moore

THE last few decades have witnessed the introduction of many new nonmetallic mineral products and changes in the use of many of those already well known. Among these is diatomite, formerly employed as a mild abrasive and, at one time, as the absorbent material in dynamite. Now nearly 100,000 tons a year are mined and milled into such things as filter aids, cement admixtures, insulants, fillers, absorbents, cosmetics, cleansers, etc. Pumice, commonly regarded as only an abrasive, is now also employed as an insulant, as light-weight aggregate and as a concrete admixture. With increasing use of insulants, light-weight aggregates, and acoustic stuccos and plasters in the building trades, both these mate-rials should find increased application. Very large deposits occur in eastern Oregon and have been studied by the U. S. Geological Survey in cooperation with the Oregon State Mining Board.

Jan 1, 1934

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".&apos;!&apos; the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.&apos;-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"&apos; supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,&apos;" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".&apos;*,"&apos; Soba1,&apos;" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D&apos;—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2&apos;—distance from copper-lead interface, cm (2&apos; = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick&apos;s first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.&apos; Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan&apos; has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock&apos; found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By L. A. Roe, E. A. Elevatorski

Wollastonite, named after William H. Wollaston, an English chemist, is a calcium metasilicate, CaSiO3; CaO: 48.30%, SiO2: 51.70%. It has a short history as an industrial mineral. The earliest production of wollastonite is reported to be from a deposit near Code Siding, located north of Randsburg, CA. At this locality small tonnages of wollastonite were quarried during 1933-34 and 1938-41, and processed into mineral wool. This operation was largely experimental and virtually no United States production was again reported until the 1950s when a large deposit near Willsboro, NY, was developed by the Cabot Corp. A processing plant was placed onstream in 1953, with nearly continuous production to date. It is currently operated by NYCO, a division of Processed Minerals, Inc. Since 1958, wollastonite deposits in the Little and Big Maria Mountains of Riverside County, and in the Panamint Range of Inyo County, both in California, have operated intermittently for production of both ornamental and commercial wollastonite. During 1980, the United States was the major producing country, furnishing about 75% of the world&apos;s output. Current production comes from Finland, Mexico, India, and Kenya. Small amounts have been shipped intermittently from the USSR, New Zealand, Republic of the Sudan, Republic of South Africa, and Namibia (South-West Africa). The principal use of wollastonite is in the manufacture of plastics. Other uses are for paints, ceramics, adhesives, fluxes, glazes, thermal insulation board, and refractory products. Mineralogy Pure wollastonite, CaSiO3, has the composition of 48.3% CaO and 51.7% SiO2. However, it is seldom found in the pure state due to the ease with which it takes into solution the metasilicates of manganese, magnesium, iron, and strontium. Predominantly, wollastonite occurs as a contact metamorphic deposit forming between limestones and igneous rocks. Commonly associated minerals are garnet, diopside, epidote, calcite, and quartz. It has a specific gravity of 2.8 to 3.0, and hardness of 4.5 to 5 on Mohs&apos; scale. When pure, it has a brilliant white color, but with impurities it may be grayish or brownish. Luster is vitreous to pearly. Melting point of wollastonite is about 1540ºC. Wollastonite occurs in coarse-bladed masses, rarely showing good crystal form. It is usually acicular or fibrous, even in the smallest of particles. The most unique property of crushed and ground wollastonite is its cleavage. Fragments of crushed wollastonite tend to be needle-shaped, imparting a high strength, and this property is the basis for many of its uses. The fiber lengths are commonly in the ratio of 7 or 8 to 1, length to diameter. The average diameter of wollastonite is 3.5 µm. Some crystals of wollastonite fluoresce under short-wave or longwave ultraviolet light, or both, with colors ranging from yellow-orange to pink-orange. Specimens may also show phosphorescence. The acicularity of wollastonite is a property of considerable importance to the marketplace. The plastics industry makes utilization of high aspect ratio grades of wollastonite (20:1) for reinforcing thermoplastics and thermoset polymer compounds. The naturally high pH of 9.9 (10% water slurry) is a prime property to the coatings industry. The coatings industry uses milled grades of wollastonite as a pH stabilizer in interior and exterior PVA and acrylic latex systems. Processed wollastonite can have a G.E. brightness of 90 to 93. Chemically, wollastonite is inert and this property makes it useful as a filler and reinforcing agent. There are two polymorphs of calcium silicates: wollastonite, a low temperature form, and pseudowollastonite, a high temperature

Jan 1, 1983

By William H. Morris

At the Glen Summit meeting, the question of controlling the silicon in pig-iron WAS raised; and as this has been deemed by most furnace-men for years past a matter of special difficulty, an account of our experience in the matter may be of interest. When running on mill-iron, some years ago, we aimed to keep

Jan 1, 1893

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.&apos; The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By J. T. Eash, E. M. Wise

Platinum and palladium are the most generally useful, most ductile and least rare members of the platinum family. They have many important applications in the pure state but for other applications it is frequently desirable to harden them and otherwise modify their properties by alloying small amounts of the other platinum group metals with them. These alloys are frequently required to withstand very drastic forming operations and to possess certain mechanical properties to fulfill specific requirements. For these reasons a knowledge of the tensile properties and annealing characteristics of pure platinum and palladium as well as their more useful commercial alloys is important to the user and the fabricator. The present work was undertaken to fill this need. Rather brief (5 min.) annealing treatments were employed to render the data of maximum practical value and all tests were conducted upon 0.050-in. dia. wire, initially reduced 50 per cent in area by cold drawing, for the same reason. Conclusions 1. Pure (thermocouple grade) platinum reduced 50 per. cent by cold drawing exhibits the following tensile properties: ultimate tensile strength, 36,000 lb. per sq. in.; proportional limit, 27,000 lb. per sq. in.; elongation, 2.5 per cent in 2 in.; reduction in area, 95 per cent. When fully annealed by treatment at 1100°C. its properties are: ultimate tensile strength, 20,700 lb. per sq. in.; elongation, 30 per cent in 2 in.; reduction in area, 93 per cent. 2. The addition of alloying elements in moderate amounts markedly increases the strength and annealing temperature without much detriment to the ductility. The behavior and properties of variously hardened platinum alloys are considered in some detail. The behavior of a 20 per cent iridium

Jan 1, 1935

By J. T. Eash, E. M. Wise

Platinum and palladium are the most generally useful, most ductile and least rare members of the platinum family. They have many important applications in the pure state but for other applications it is frequently desirable to harden them and otherwise modify their properties by alloying small amounts of the other platinum group metals with them. These alloys are frequently required to withstand very drastic forming operations and to possess certain mechanical properties to fulfill specific requirements. For these reasons a knowledge of the tensile properties and annealing characteristics of pure platinum and palladium as well as their more useful commercial alloys is important to the user and the fabricator. The present work was undertaken to fill this need. Rather brief (5 min.) annealing treatments were employed to render the data of maximum practical value and all tests were conducted upon 0.050-in. dia. wire, initially reduced 50 per cent in area by cold drawing, for the same reason. Conclusions 1. Pure (thermocouple grade) platinum reduced 50 per. cent by cold drawing exhibits the following tensile properties: ultimate tensile strength, 36,000 lb. per sq. in.; proportional limit, 27,000 lb. per sq. in.; elongation, 2.5 per cent in 2 in.; reduction in area, 95 per cent. When fully annealed by treatment at 1100°C. its properties are: ultimate tensile strength, 20,700 lb. per sq. in.; elongation, 30 per cent in 2 in.; reduction in area, 93 per cent. 2. The addition of alloying elements in moderate amounts markedly increases the strength and annealing temperature without much detriment to the ductility. The behavior and properties of variously hardened platinum alloys are considered in some detail. The behavior of a 20 per cent iridium

Jan 1, 1935

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923