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By Richard Franchot

DISCUSSION of a paper is sometimes more in-teresting in what has not been said than in what is said. In the present case the paper is mainly directed to certain thermo-dynamic relation-ships in the blast furnace. Careful reading of the dis-cussion fails to show a single use of the term, heat unit, or its equivalent. If we wish to know very-much about the furnace action it is necessary to count calories or B.t.u. Nothing much is. said about the availability of heat at high temperatures, although it will be generally admitted that in seeking underlying limiting factors in the furnace economy the hearth heat relations offer-the most promising clues. Those discussing the paper, with exceptions of course, apparently have failed to recognize an outstand-ing fact. It is a fact that the heat actually generated by the air oxygen in CO formation (including the blast heat) is in excess, after charging off radiation, etc., by from 70 to .90 per cent over the heat absorbed in melting the iron and slag and calcining the stone reduction by CO absorbing no heat. The fact stands out as plainly as does the fact that the furnace functions largely as a gas producer. The surplus heat is there. It is in the picture. Why not take a look at it, face the fact? That the surplus heat is necessitated by the hearth conditions admits of very little if any doubt. The furnace is really two separate pieces of apparatus: the hearth, doing certain work, and the superimposed shaft, doing certain other work. The combustion of fuel in the hearth, primarily serving the hearth pur-poses, generates much more heat and gas than the shaft requires, or can use, in smelting work. The result is surplus heat makes still more gas in the heat-absorbing reaction between CO, and coke; what is left of the surplus going to top heat. Here we have a simple yet adequate sketch of the furnace action. Having obtained a fairly comprehensive view of the existing heat relations of both hearth and shaft, the way to improvement seems quite plain. Either do more of the work above the hearth or put more heat into the hearth. Since there is already a great surplus of heat above the hearth, probably little needs to be done by way of increasing the proportion of the work done in the shaft. The shaft can, however, probably do much more work than it is now doing provided that a way, can be found to get more work, done in the hearth. The hearth heat is nicely balanced. Losses by radiation and water cooling and other losses are already taken care of. Any increase of hearth heat development could be utilized in taking care of increased smelting work. Aside from the possibility of increased blast heat, there is one sure way of putting more heat into the hearth, and this is to blow more air. And since the shaft already has more gas than it needs, the increased gas resulting from the greater blast volume can be withdrawn from the bosh after it has done its work in the hearth. Now an increase of burden will cool the shaft, cut down solution loss and thereby supply addi-tional coke in the hearth to burn with the additional air blown. The hearth heat per pound of coke charged will be proportionately increased. The balance between hearth and shaft will be better. Gruener's ideal will be more nearly attained, if not exceeded. Most inter-esting of all perhaps, the more the burden is increased, the more coke will reach the hearth and the more burden can be added. The effect is to be cumulative.

Jan 3, 1927

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors' paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.'' The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors' 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)' D = 3.55 x 10"3 exp (-5550/)' D = 4.3 x 10"3 exp (-5620/1')' Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By D. Muraoka

Introduction Soda ash, anhydrous sodium carbonate, is produced from underground trona deposits occurring in the Green River Basin of southwestern Wyoming. Stauffer Chemical Co. of Wyoming, a jointly owned subsidiary of Stauffer Chemical Co. and Rocky Mountain Energy Co., mines the trona and processes it into high-purity soda ash. Stauffer Wyoming has been in operation since 1962 with a current production capacity of about 1.8 Mt (2 million st) per year of soda ash. The refinery has five parallel operating trains using the monohydrate process which is a series of chemical processing unit operations described below. Screening and Crushing The mined trona is brought to the surface in two counterbalancing ore skips. The ore is initially screened with refinery feed (less than peagravel size material) entering the process. Oversize is conveyed to an outdoor stockpile. Ore is recycled from under the stockpile via cone feeders as the refinery needs require. The ore is conveyed to hammer type crushers and screened. The refinery feed enters the process and the oversize is recycled to the crushers. Calcining The first step in refining trona to soda ash is calcining the trona ore. This is accomplished in concurrent flow, rotary kilns that are direct fired with natural gas. [2 (Na CO NaHCO 2H O) Heat 3Na CO + 5H20 + CO 2 3~3~ 2 ~~2 32] The trona ore is fed to the kiln at the burner end and is intimately mixed with the hot exhaust gases from the burner. Direct contact with the flame is avoided. The ore moves down the kiln by gravity and rotation aided by the kiln's internal lifters. The exhaust gases are cleaned to 99 + % particulate removal and discharged to the atmosphere. Dissolving the Calcined Trona The calcined trona is conveyed from the kiln discharge to a rotary drum dissolver where it is mixed with water and weak solution (unsaturated solution of calcined trona in water). The calcined trona is soluble whereas the impurities, primarily shale, are insoluble. The discharge from the dissolver is a slurry containing saturated solution (about 30% dissolved calcined trona in water), some undissolved calcined trona, insoluble impurities, and organic impurities. The dissolver discharge enters a rake classifier that makes the first solid/liquid separation in the process by removing the heavy undissolved material from the saturated solution. This undissolved material is conveyed to a second rotary drum dissolver and mixed with water to dissolve any remaining calcined trona. The secondary dissolver discharges to a second rake classifier that separates the solids from the liquid. The solids are now primarily insoluble impurities with very little unrecovered calcined trona. These wastes are conveyed to evaporation ponds for disposal. The liquid from the secondary rake is recycled to the primary dissolvers' weak solution system. Returning to the primary rake classifier, the saturated solution which contains suspended insoluble muds is pumped to a thickener. Flocculant is added to aid settling of the suspended muds. The flocculated muds are collected at the bottom of the thickener and pumped to vacuum cloth filters. The adhering saturated solution is separated from the muds that remain on the filter cloth. The recovered solution is returned to the dissolvers' weak solution system. The muds are reslurried and pumped to the evaporation ponds for disposal. Saturated solution, containing some suspended insoluble muds along with the organic impurities, overflows the thickener. Filtering the Saturated Solution The saturated solution overflowing the thickener enters a holding tank where it is pumped to a bank of pressure leaf filters. The suspended muds are captured on the filter leaves while the cleaned saturated solution is pumped to polishing filters. The polishing filters are also leaf pressure type, intended to remove any suspended solids that may pass the primary filters. Organic impurities are removed with activated carbon. The purified solution is now free of insoluble muds and has most of the organic impurities removed. Crystallizing and Drying the Monohydrate The purified saturated solution is pumped to evaporative crystallizers. The solution is circulated from the crystallizer vessel through a heat exchanger. Indirect contact with steam in the heat exchanger causes the saturated solution to boil, thus crystallizing the soda ash in its monohydrate form. Slurry crystal density is maintained in the crystallizer by simulta¬neous feed of fresh saturated solution and drawoff of the slurry.

Jan 1, 1986

By S. Stopek, E. D. Hinkley, R. H. Rediker

Epitaxial heterojunctions have been prepared by melting the lower -melting-point semiconductor of the interface between two dijferent semiconductors. when the temperature is reduced, the melted material recrystallizes, having alloyed into the higher -melting-point semiconditctor. The electrical and elcctro-optical properties of such single-crystal heterojunctions between GaAs and Gash and between p-type InAs and n-type Gash are the subject of this paper. The forward current varies as exp (AV), where A is substantially independent of temperatuve. For Gds-Gash heterojunctions at temperatures above, 370°K, if the current-voltage relationship were to he expressed as exp (qV/nkT), then n would he less than unity. The injection luminescence associated with forward current is, for the most part, characteristic. of the lower bandgap semicondutctor. These results can he explained by carrier injection into the lower bandgap semiconductor by tunneling through a barrier at the interface. The photovoltaic effect measured for incident photons having energies in the range between the bandgaps of the two semiconductors is much smaller than that produced by higher-energy photon The smallness of this between -the-gap photovoltaic response can he explained by the low probability for penetration of the barrier by the carriers produced in the smaller -bandgap semiconductor. THE technique of interface alloying has been used to produce single-crystal junctions between dissimilar semiconductors.' Oriented wafers are placed on a carbon heater strip, Fig. 1. so that semiconductor S1, which has the lower melting point, is supported by semiconductor S2. Electrical current passed through the heater strip produces a temperature gradient such that S2 is at a higher temperature than S1. As the temperature is raised the lower face of S1 begins to melt. Before the entire wafer can melt, however, the heater-strip current is turned off and, as illustrated in Fig. l. the melted portion recrystallizes, having alloyed into S2. Junctions have been fabricated by the above procedure between GaAs and germanium, between GaAs and GaSb, and between InAs and GaSb. Mroczkowski, Lavine. and Gatos have described the metallurgical and chemical aspects of the GaAs-Ge junction.2 The transition from GaAs to germanium is not monotonic and a portion of the recrystallized region consists of the GaAs-Ge eutectic. Since gallium is an acceptor and arsenic is a donor in germanium, since germanium dopes GaAs, and since the electrical properties of the GaAs-Ge eutectic have not been investigated, any interpretation of the electrical characteristics in terms of simple heterojunction theory would be incorrect. That the rectification of GaAs-Ge heterojunctions is not a property of the impurity doping of the GaAs or the germanium, but is most probably due to the impurity distribution in the recrystallized region, is clear from the fact that forward conduction occurred for all the GaAs-Ge interface-alloy junctions (whether they be n-n,n-p. p-n. or p-p) when the germanium was biased positively. The electrical characteristics of these GaAs-Ge heterojunctions will not be discussed further in this paper. Electron-beam microprobe analysis of GaAs-GaSb heterojunctions showed that the transition from arsenic to antimony atoms was without structure. and that the transition occurred within a 2 to 3 region.' In this paper we will describe the electrical properties of the GaAs-GaSb heterojunctions as well as electrical and electro-optical properties of the InAs-GaSb heterojunctions. A band model for the junction will be proposed which can explain these properties. ELECTRICAL PROPERTIES OF GaAs-GaSb HETEROJUNCTIONS After interface alloying. in preparation for the electrical and electro-optical experiments, ohmic contacts were made by conventional means. For example. Kovar tabs clad with tin were alloyed to n-GaAs or similar tabs clad with Au-Zn were alloyed to p-GaAs. The units were mounted and then etched. All four combinations of conductivity types

Jan 1, 1965

By Oscar Weiss

STILFONTEIN and surrounding areas gave nega-tive results in all prospecting attempts since about 1904 when Goerz and Co., a forerunner of Union Corporation Ltd., first drilled in the region and on the farm Stilfontein. Subsequent efforts by African and European Investments Co. and Anglo American Corp. from 1934-37 were completely unsuccessful. Holes drilled by these companies on the farms Riet-fontein, Hessie, and Palmietfontein were stopped in the Lower Witwatersrand system without finding payable reefs. The results of gravimeter, ground magnetometer, and aerial magnetometer surveys are presented in the area, in and around the new Stilfontein Gold Mine, in the Klerksdorp District of the Transvaal in the Union of South Africa. The gravimeter and ground magnetic surveys were completed in 1947—48. The gravity anomalies suggested a block of Upper Witwatersrand quartzites faulted-up between denser rocks of dolomite and Ventersdorp lava. Boreholes S.T. 1, 2, and 3 were drilled in 1948 and, after penetrating the dolomite and Ventersdorp lava, entered Upper Witwatersrand quartzites and intersected the Gold Estates Reef and Vaal Reef. Subsequent drilling delineated the suboutcrop of the Vaal Reef and determined the main structure of this horizon. The gold content of the Vaal Reef was highly payable and shaft sinking is now in progress. The Stilfontein Gold Mining Co. has been formed and, up to date, f5,000,000 capital has been raised for plant, shaft sinking, and development. The payable Vaal Reef horizon extends further south from Stilfontein, the reef occurring at increasing depths. It is possible that at least another mine may be established on these deeper horizons. The farm Stilfontein 39 is situated in the Klerksdorp District of the Transvaal. This farm and the surrounding areas have been subjected to repeated programs of prospecting dating back to about 1904, when Goerz and Co., the forerunner of Union Corporation, Ltd., first drilled on the farm and in the surrounding areas. From 1934-37, numerous boreholes were drilled on the neighboring farms, Riet-fontein. Hessie. and Palmietfontein, by African and European Investment Co. and Anglo American Corp. All these efforts were completely unsuccessful, and nobody suspected any possible gold-bearing area on Stilfontein until about 1947, when a gravity traverse run by B. D. Maree on the main road, showed a negative gravity anomaly. During 1947-48, the writer's organization completed gravimeter and magnetic surveys on Stilfontein and Rieffontein. An area of negative gravity anomalies was mapped, and it was suggested that this could be caused by blocks of Upper Witwatersrand quartzites, of the average density of 2.65, faulted up between dolomites and Ventersdorp lavas, the density of both of these rocks being 2.8. Fig. 1 shows the geology of the area as mapped by L. T. Nel of the Geological Survey of South Africa. The boreholes on Stilfontein, with the exception of a single hole of Goerz and Co., were drilled after the completion of the geophysical survey. The grouping of the first boreholes S.T. 1, 2, 3, 4, 5, and 6, clearly shows that these were located in the zone of negative gravity anomalies. Fig. 2 shows the gravity anomaly contours. Fig. 3 shows two sections across the gravity anomaly, together with the corresponding geological sections as obtained from boreholes. The close relation between gravity values and thickness of dolomite plus Ventersdorp lavas is striking. The two latter formations having the same density (2.8), act as one mass as far as gravity effects are concerned. Fig. 4 shows the magnetic anomalies observed on the ground by vertical magnetometers and at 500 ft abbve mean ground level by aerial magnetometer. The latter are anomalies of the total magnetic intensity. The magnetic results show that, on the farm Rietfontein and on the northern half of Stilfontein. Lower Witwatersrand magnetic shales were to be expected at relatively shallow depths. As the strongly

Jan 1, 1952

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid iron alloys containing chromium and nickel has been measured in the temperature range 1550° to 1700°C at nitrogen pressures to 1 ah. The solubility surface has been determined for the iron corner of the liquid metallic ternary to 21 pct Cr and 11 pct Ni. The nitrogen solubility increases markedly with increasing chromium concentration. The effect of nickel and the bilinear effect of chromium and nickel are less pronounced. The solubility data are presented, and interaction coefficients are determined from them. THE solubility of nitrogen has been determined in liquid Fe-Cr-Ni binary and ternary alloys. The work in this laboratory has been directed toward a relatively limited composition range, that is to 20 pct Cr and 10 pct Ni. Humbert and Elliott1 studied the entire ternary; but their investigation was, understandably, limited in this region. The region considered here is of the greatest commercial interest. Knowledge of the solubility in these alloys is important for accurate control of the nitrogen levels in various stainless alloys. Also, the solution behavior is of theoretical interest because of its deviations from ideal dilute solution rules at moderate chromium levels. The nitrogen solubility in the iron binaries has been reviewed extensively by Pehlke and Elliott,2 particularly with respect to the dilute solution interaction parameters. More recently, there has been some interest in accurate descriptions of solute interactions in non-dilute solutions. Most of the investigators have adopted a power series fit to accommodate any non-linearity of the data. The Taylor series expansion is adopted here, using Scimar's notation3 for the interaction coefficients. An alternate method, instead of requiring higher-order expansions, is to restrict the range of the composition variables. A planar solubility surface may be fitted to the data and its range of validity determined. If the axes of this region are displaced from the usual origin—the solvent pure iron—a change in standard state is required for the solution reaction. The standard state for nitrogen in iron is commonly taken as the hypothetical 1 wt pct solution of nitrogen in pure iron. However, for an alloy of appreciable solute concentration, e.g., 13 pct Cr or 18 pct Cr-8 pct Ni, it would be convenient to use that base composition as the solvent and redefine the solution reaction in terms of that particular solvent. A brief derivation follows, defining the free energy of solution in an alloy solvent. Following the treatment by Darken and Gurry,4 for a nitrogen pressure of 1 atm: N (pure component) = N (1 wt pct in solvent) [l] AG=RT ln100/ wt pct N in solvent Taking this reaction for an alloy solvent less the same reaction for a pure iron solvent the relation between nitrogen in pure iron and an alloy is: N (1 wt pct in Fe) = N (1 wt pct in alloy) [2] AG = RT[ln(wt pct N in Fe) - ln(wt pct N in alloy)] Adding ½ N2(g) to each side and subtracting N (1 wt pct in Fe) = ½N2(g), the total free energy for solution of nitrogen in an alloy, referred to nitrogen at infinite dilution, is given by: ½N2 (g) = N (wt pct in alloy) L3] AG°3 = -RT ln(wt pct N in alloy )PN =1 atm Interaction parameters have their usual meaning when ?G°/RT is differentiated with respect to the proper composition coordinate. If desired, the dilute alloy treatment may be utilized with the new reference composition as the solvent. This has. indeed, been done by Small and pehlke5 in their analysis of nitrogen solution in liquid 18-8 alloys. The Sieverts' technique was used for this investigation on an apparatus previously described.6 The materials used in this program were: Ferrovac-E iron, 99.95 pct, Crucible Steel Co.: chromium, 99.95 pct, Union Carbide Metals Co.; nickel, 99.9 pct, International Nickel Co. Recrystallized alumina crucibles were used with no evidence of crucible-melt reaction. RESULTS The locations of the ternary compositions investigated are shown in Fig. 1. The data of Turnock7 and small8 have been alluded to in other papers.5'6 There were no departures from Sieverts' law observed for

Jan 1, 1969

By W. A. Hockings, M. E. Volin, A. L. Mular

Batch grinding tests at short times were made in a laboratory rod mill with 10 x 14 mesh quartzite in corn syrup-water mixtures of varying viscosity. The weight fraction broken and size modulus were found to be independent of viscosity up to 20 cp, but at higher viscosities breakage of the feed decreased while the size modulus increased. The mechanisms of the effect of viscosity are discussed on the basis of particle dynamics. The effect of viscosity of the suspending medium on grinding has not been accorded much attention, although both wet and dry grinding are used in bene-ficiation processes and the viscosities of water and air differ greatly. schweyerl investigated the rates of grinding of quartzite in a pebble mill with air, water and glycerol as the suspending media and found the rate in terms of new surface developed per thousand revolutions of the mill to be constant and dependent on viscosity up to 20,000 rev, but to decrease and become independent of viscosity for longer grinding times. Based on considerations of the drag forces exerted on suspended particles and on the grinding media under turbulent and laminar flow conditions, viscosity can be expected to inhibit the rate of grinding in a given system as it changes the flow conditions from turbulent to laminar. The objective of this study was to determine the effect of viscosity of the suspending fluid in the batch grinding of a homogeneous feed of uniform size for short residence times, a region of more practical interest than the long times investigated by Schweyer. In actual grinding operations, the viscosity of the fluid does not change, but the consistency (apparent viscosity) of the pulp increases with additions of fines. In this study the consistency of the pulp was not measured because it was thought that the grinding times were too short to alter the apparent viscosity appreciably.* *Minus 200 mesh quartz at 65% solids has an apparent viscosity of about 25 cp as measured by a simple consistometer. Personal communication from D. F. Kelsall to A. L. Mular. For the purposes of this study, the effect of viscosity on grinding can be shown sufficiently well on the basis of the cumulative weight fraction finer than the feed size at any time, and the size modulus, ku, of the finer than feed sizes. The parameter, ku, is obtained from a form of the Gaudin-Schuhmann equation. METHOD AND MATERIAL The grinding tests were accomplished in a laboratory rod mill 10-1/2 in. long and 8 in. bore with a 20-lb rod charge consisting of two 1-in., eight 3/4-in., eight 1/2-in., and eight 1/4-in. diam rods. The mill speed was 43.2 rpm. Charges of 400 g 10 x 14 mesh Wisconsin quartzite** were ground for times of 60, **Courtesy of Minnesota Mining and Mfg. Co. 120, 180 and 240 sec in 500 cc of fluid made up of corn syrup and water in measured proportions. The temperature of the pulp was measured immediately upon completion of grinding, and the size distribution of the quartzite was determined by a wash-wet-dry screening technique. Corn syrup was chosen because of its high viscosity and ideal viscous behavior, and also because its density is not greatly different from that of water. The viscosity of each fluid mixture was measured with an Ostwald viscometer at 25 C. and a correction was made for the temperature of the pulp according to tabulated values for sucrose solutions. The density differences were so small that they probably did not significantly affect breakage. RESULTS AND DISCUSSION The conditions of the grinding tests, computed viscosities, weight fractions finer than the feed size and values of a and ku are listed in Table I. The values of a and ku were taken from the linear portions of the log-log plots of cumulative weight fraction finer vs size for the various grinding times. The plots for tests in fluids of average viscosity 8.6 cp are shown in Fig. 1. In general all of the sets of curves were linear throughout most of the size

Jan 1, 1965

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By Kenneth Schellinger

THE terms surface tension and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit, of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid: gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct'" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the min- erals present. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid:liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1953

By Lawrence H. Van Vlack, Otto K. Riegger, Gerald I. Madden

The microstructural variations of periclase (MgO) in the presence of oxide liquids are examined under the steelmaking variables of: 1) temperature, 2) liquid composition, and 3) FeO additions under different oxidation levels. Attention is given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. Silicate liquids penetrate more extensively between individual periclase grains than do liquids containing high percentages of Fe2O3 Higher MgO solubilities in the liquid and lower MgO contents of the solid favor more rapid grain growth. The presence of a second solid phase reduces the periclase grain growth rate and increases the amount of the solid-to-solid contact within the oxide microstructures at high temperatures. The service suitability of a refractory depends on many factors. Two are of major importance and include 1) the thermal resistance to melting, and 2) the mechanical resistance to loads at service temperatures. Neither is a simple consequence of the service temperatures because service conditions will alter compositions, produce partial melting, and induee phase changes. Consequently, the equilibrium phase relationships have been rather thoroughly studied and give a knowledge of the thermal resistance to melting, but do not give full information about the mechanical properties because two refractories with the same types and quantities of phase may have different microstructures. Although variations of microstructures with time, temperature, and composition have been subjects for extensive investigation in metals, only a limited amount of comparable microstructural work has been performed for refractory materials.' This study was an attempt to evaluate some of the consequences of service parameters upon the microstructures of refractories so that bases may be established for the analyzing of high temperature mechanical properties. Periclase (MgO) was chosen as the refractory oxide; variables included those which are encountered under steelmaking conditions such as 1) temperature, 2) liquid composition, and 3) FeO additions under various oxidation levels. Specific attention was given to the distribution of the phases, both liquid and solid, and to the growth of individual crystalline grains. The most closely related work on microstructures of polyphase materials is that of Van Vlack and Rieg-ger2 on the microstructure of magnesiowüstite [(Mg,Fe)O] in the presence of silica. In that work which pertained to solid solutions with less than 40 pct MgO, most of the quantitative work was performed on FeO microstructures. The chief conclusions concerning these relatively low-melting oxide solids were as follows: 1) the rate of crystalline grain growth is inversely proportional to the grain diameter, 2) grain growth proceeds more rapidly at higher temperatures but is slightly retarded by additional liquid content, and 3) a Silicate-containing liquid penetrates as a film between the individual magnesiowüstite grains independent of time, temperature, amount of liquid, or the MgO/ FeO ratio. The above observations are in contrast to prior work3 on the microstructure of silica in the presence of iron oxide-containing liquids where the liquid does not penetrate as a complete film between solid grains. The phase relationships for the compositions of the present work are shown in Fig. 1 which is a summary of the work of several investigators.4 Of importance is the fact that CaO forms a more stable structure with SiO2 and Al2O3 than do either MgO or FeO. The oxygen potential has little effect on periclase unless iron oxide is also present. The iron oxide is ferrous at moderately low oxygen levels, changing to ferric as the Oxygen potential is increased so the spinels, magnetite, and magesioferrite are formed.5 These two phases are relatively stable in air at steelmaking temperatures. I) EXPERIMENTAL PROCEDURE ractory were made with reagent grade Oxides. The magnesium oxide used was 99 pct MgO after ignition, and the iron oxide raw material had a minimum content of 99 pet Fe2O3. The CaO, SiO2, and A12O3 were also reagent grade raw materials. After mixing, the required compositions were pressed into pellets at a minimum pressure of 5000 psi to insure compaction of the raw materials and prevent excess void content. A silicon carbide element tube furnace was used with thermocouple control for sin-

Jan 1, 1963

By Don M. Jackson, Robert W. Howard

Techniques for the epilaxial growth of single -crystal silicon carbide films on silicon were developed. The vapor-phase decomposition and bydrogen reduction of silicon tetrachloride (SiC14) and Propane (C3H8) resulted in clear films of silicon carbide, lip to seveval microns in thickness. The growth took place in a horizontal . silicon epilaxial reactor at 1100°C (pyrometer) at a rate of- 3000Å per minute. Electron diffraction and X-ray diffraction studies demonstrated that the films were single-cyrstal, ß -phase, or cubic silicon carbide. SiO2 film were used to mask areas of the silicon sur-lace in order that the silicon carbide might be grown in controlled geometries. Both n- and p-type films were grown on p-type silicon waters.. Heavily doped silicon films of the same conductivity type as the silicon carbide films were deposited over the silicon carbide in order to affect better probe contact to the structures. when n-type silicon carbide mesas were grown on p-type silicon substrates the de vollage-current relationships between films and substrates were that of junction diodes. These diodes showed a sensitivity to while light ill that the incident light increased forward- and reverse-satro,ation currents, P-type silicon carbide mesas grown on p-type silicon were ohmic rather than rectifying in their voltage -current relationship. No conclusions could he reached concerning heterojunc-tiou rectification in the structure. SILICON carbide is a semiconductor with many interesting properties. It decomposes at temperatures above 2200°C.1 It occurs in two general crys-tallographic forms—hexagonal (a Sic) and cubic (ß Sic)—with the cubic form having a forbidden-gap energy of 2.32 ev and the hexagonal form (specifically the 6H polytype) a gap energy of 2.86 ev.3 It behaves as an extrinsic semiconductor at temperatures approaching 5003C. It has been shown to have a high resistance to radiation damage4 and p-n junctions formed in Sic have been shown to radiate visible light under forward- or reverse-bias conditions. Epitaxial silicon carbide on silicon carbide has been successfully grown through the use of a variety of techniques, such as gaseous cracking of SiCL4 and CC4, nearly all of which require a deposition temperature above 1500°C.6 This paper will cover very recent work on the gas-phase deposition of highly ordered films of silicon carbide on high-quality silicon single-crystal substrates. The films have been shown to ex- hibit junction-rectification properties when geometrically isolated regions are electrically biased with reference to the silicon substrate. There will be no discussion of the mechanism of heterojunction rectification, but the methods of film fabrication, geometry control, and structural evaluations will be covered in detail. Electron diffraction, X-ray diffraction, and diode electrical properties were used to characterize the films and the junctions. GAS-PHASE DEPOSITION OF Sic The techniques for the deposition of silicon carbide films were a logical outgrowth of the standard silicon epitaxial process. The major premise followed was that, for any film to nucleate in an ordered fashion where there is considerable mismatch in lattice parameters (in this case 22 pct), an extremely clean, damage-free substrate surface must be presented to the gas stream. Thus a standard gas-phase HCl etching step was used to prepare the substrates for growth. A minimum of 5 µ of substrate-surface material was removed prior to the deposition of Sic overgrowth films. The techniques used for growing silicon carbide films were those of growing silicon alone, with the added injection of a hydrocarbon gas into the hydrogen and silicon tetrachloride gas stream. The hydrocarbon gases used thus far have been research-grade (99.99 pct) methane (CH4) and propane (C3H8). Propane ultimately gave the best results. The gas flows were controlled through a panel shown schematically in Fig. 1. A hydrogen main stream of 30 liters per min passed through the horizontal quartz-tube epitaxial reactor, while SiC14, C3H8, HC1, and doping gases were injected as side streams. The

Jan 1, 1965

By Kenneth Schellinger

THE terms surface tension and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit, of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid: gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct'" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the min- erals present. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid:liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1953

By Martti E. Maliniemi

The Svappavaara mine is located 47 km southeast of Kiruna C. The ore deposit now being worked, Leveäniemi, belongs to Luossavaara- Kiirunavaara AB (LKAB) and is the company's, and also Sweden's, third biggest mine after Kiirunavaara and Malmberget. The distance by rail to the Norwegian port of Narvik is 214 km and to Lulei on the Gulf of Bothnia 340 km (Fig. 1). The village of Svappavaara has about 800 inhabitants. The climate is arctic in character. The temperature during the months of December to February is about -20º to -35ºC, and the ground is covered by a blanket of snow for about eight months of the year. The brief, intensive summer often arrives with startling speed, bringing both sunshine and warmth. HISTORICAL BACKGROUND Mining operations took place in Svappavaara as far back as 300 years ago. During the period 1655-1684, copper ore was taken from the deposit called Gruvberget in the vicinity of the village. The total production of raw copper was probably about 1,045 tons. During the 18th and 19th centuries, several attempts were made to extract iron ore from the numerous deposits found within the district. These brave attempts, however, were foiled by the high phosphorus contents and the enormous transport difficulties. The present-day mine fields in Leveäniemi were discovered in 1897. At that time, it was difficult to determine the size and value of the deposit because of the thickness of the soil cover (3 to 15 m) and the

Jan 1, 1969

By Clark A. Sumner, D. Arthur Burnham

A process for recovery of greater than 99% of the copper contained in acid leach solutions by sulfide precipitation using hydrogen sulfide as a hydrometallurgical reagent has been developed. The process incorporates the concept of hydrogen sulfide addition to recycled copper sulfide solids in a turbulent flow area where further precipitation or agglomeration occurs to increase the effective particle size of the copper sulfide precipitate. Because the recycled solids provide a larger number of particles upon which momentary excesses of hydrogen sulfide are absorbed, oversulfidization of the product is prevented. Copper sulfide precipitates produced in this manner in a laboratory test reactor showed greatly improved physical characteristics compared to copper sulfide precipitates obtained by conventional direct precipitation in which H2S is bubbled directly into acid leach liquor. Copper sulfide precipitates were evaluated and compared by use of filtration tests and settling rate studies. Electron microscopic examination of the solids confirmed the presence of larger particles in reactor-precipitated copper sulfide. Flotation was examined as an alternative to filtration for recovery of CuS precipitates and was found to achieve complete CuS removal without addition of collector or frothing reagents in a period of 2 min. In the same test reactor, a rapidly floatable CuS precipitate was also formed by mixing H2S with acid liquors used to leach crushed copper oxide-copper sulfide ore (LPF process). In the presence of gangue from the crushed ore, flotation of both natural and reactor-produced copper sulfides resulted in recovery of better than 90% of the copper contained in the crushed ore.

Jan 1, 1974

By B. E. Morgan, C. K. Dumbauld

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic' displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. 'To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard's Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By C. K. Dumbauld, B. E. Morgan

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By K. Prins

ONE of the more pressing problems faced by the coal industry today is the development of adequate means for meeting conservation laws, particularly those involving stream pollution, in various parts of the country. Discharge of dirty coal washery water into streams and rivers is almost universally frowned upon. Many states have enacted laws carrying heavy fines to curb the practice. The Prins stream-cleaner is one of the latest machines to enter the market. It is closely related to the cyclone thickener in principle. Eleven stream-cleaners are currently operating, ranging in size from 4 to 16 in. diam. In more recent installations the water enters directly in line and on a tangent with the impeller. The impeller consists of a vertical shaft up through a packing gland and bearings, and a V-belt pulley. The lower part is a tubing fastened to the shaft above, extending through the water intake compartment and provided with six vertical flat bars welded to the tubing. Portholes are situated in the upper end of the tubing, immediately below the point where shaft and tubing join together. The portholes are placed so that they are in open communication with the upper compartment of the stream-cleaner from which the processed water is discharged. The impeller is motor driven with a wide range vari-pitch drive employed between motor and impeller. The motor is mounted vertically, and the mounting provided with a vertical hinge allowing for needed adjustment of the wide range vari-pitch drive. The dirty coal washery water entering the machine under 20 lb psi pressure, flows from the compartment above the impeller, between the impeller blades, and is whirled around in the vertical section of the impeller enclosure. The speed of the impeller supplies centrifugal force and velocity required for separating suspended solids from water. The lower part of the machine consists of a cone, whose action is similar to other machines of the same type. The underflow discharge orifice is a cold rolled steel block machined to correspond with the cone angle and allows insertion of steel tubes of different diam. On 16 in. machines a 1 ¾ in. ID vertical discharge pipe is used. Provision is made for attaching a curved section of the same diam to the vertical pipe, to which, in turn, different lengths of horizontal pipe can be connected. Curved Pipe Advantageous It has been found that a curved pipe offers resistance to discharged material flow. In addition, the rotary motion of the underflow can be easily arrested in a curved pipe. Impeller speed of the 16 in. diam machine is provided from 400 to 800 rpm. A speed of about 474 rpm is suitable for maintenance of a constant underflow in coal slurry. In one installation 5x ¼ in. coal is cleaned in a Jeffrey Baum type washer at a 225 tons per hr rate. Washer installation is of the conventional type and a drag type sludge tank is used for water clarification purposes. Capacity of the water system, including the Baum washer, is about 40,000 gal. Before placing the stream-cleaner in operation, it was necessary to flush out the entire system every five days of two shift operations. The only time the system is drained now is for repair work on the sludge conveyor or the rig. The suction line of the stream-cleaner pump terminates in a number of small branch lines located at a depth of about 4 ft above the sludge conveyor. Each branch line extends the full width of the tank and is provided with four intake ports, each one with a funnel shaped inlet projecting downward. The arrangement provides an extensive pick-up area, for dirty water, and the inlets are arranged for a low rim velocity, preventing the taking in of coarse particles. The funnels are also arranged to extend up or down in the tank. They are set to pick up -60 mesh material exclusively.' The material is a high ash and high sulphur product and thus has to be disposed in the refuse conveyor. The underflow of the stream-cleaner is discharged on top of the washery refuse which is carried in a drag type horizontal conveyor, discharging into another refuse conveyor inclined at 30º with a short horizontal loading section. Some Disadvantages The impeller inherits certain disadvantages because of the nature of its construction. Additional moving parts make it subject to wear and maintenance costs. The advantage of being able to maintain a constant speed, however, to produce desired water velocity in the machine outweighs the drawbacks. Better separation between water and solids can be obtained by regulating time of residence of water through adjustment of valves in the intake and discharge lines. The amount of fines encountered during plant operation will vary because of higher or lower moisture in coal passing over fine coal vibrating screens. Even the amount of fines picked up by underground loading machines will be inconstant. Consequently, the percentage of solids will vary in water to be processed. The velocity in the feedlines to the slurry thickeners will fluctuate, with the required water velocity lacking. Another advantage advanced for the machine is its ability to operate on 15 to 25 lb line pressures at the water intake, reducing pump power required and pump maintenance.

Jan 1, 1952

By G. D. Oxx, L. F. Coffin

The concept of using a phase that is liquid at service temperatures as a component of coatings for refractory metals has been described. The liquid, an alloy of gold and silicon, is retained on a molybdemum surface by a capillary system made of molybdenum disilicide. The coating has the advantage of good thermal shock and has a self-henling chracteristic. In order for highly stressed structures to exceed a service temperature of 2000°F, it has become apparent that a development that does not depend on the traditional iron, cobalt, or nickel-base alloy is needed. Alloys of the refractory metals, i.e., molybdenum, tungsten, tantalum. niobium (colum-bium), and rhenium are potentially useful at extremely high temperatures that more conventional alloys would never be expected to achieve. A new alloy of molybdenum has become available that has a 100-hr rupture strength of 35,000 psi at 2200°F.1 As a result of this work, it may be assumed that a material with adequate mechanical properties at 2200?F is now available. Unfortunately, this alloy and all other known alloys of the refractory metals suffer from not being; serviceable in an oxidizing atmosphere for a very long time. In order to permit general use of refractory metals at high temperatures, it is necessary to prevent destructive oxidation by appropriate alloying or by protective coatings. The liquid phase coating reported here is representative of a concept for the protection of metals that permits higher service temperatures and introduces a new group of materials for selection as coatings. Coating Requirements—Service conditions that represent potential applications for refractory metals vary considerably: however, it is possible to consider two conditions that are usually present. The refractory metal1 component must be heated to the service temperature at least once and usually frequently. When a solid coating is used, usually the coating and basis metal do not have the same coefficient of expansion. This difference causes thermal stress in the coating that is aggravated by rapid heating and cooling and eventually causes coating failure. The second consideration is the probability that there will be damage to the coating by some environmental condition. In jet engines, for example, it is expected that large particles, stones, metal parts, and so forth, will strike a bucket at high speed and cut a hole in the coating. In addition to the above considerations, the coating must also have other fundamental properties. Obviously, it must be oxidation resistant. In addi- tion, it must prevent permeation of oxygen and subsequent oxidation of the basis metal at the interface. Also, diffusion of the basis metal to the outside surface and subsequent oxidation there must be prevented. Finally, the coating must not react with the basis metal to form a weak bond at the interface. It should be noted that the coating need not support a load: it must only remain intact. Liquid Phase Coating Design Factors—In the use of a liquid as a principal coating constituent, it would be expected that the two service conditions mentioned above would be satisfied. A liquid would flow under the influence of the thermal strain developed by coating-basis metal expansion mismatch such that failure from this source would not be expected to occur. It is also probable that the ability of a liquid to flow would provide a self-healing effect. Thus, damage caused by particles in the atmosphere would be repaired. A third advantage is evident in that vapor pressure rather than melting point limits the service temperature. This latter advantage permits use of low melting but oxidation resistant metals such as gold or copper that would be quite useless if the solid state was required. A low viscosity liquid alone. however, is a totally unsuitable coating because it will simply flow off a component, particularly under the influence of a high acceleration field. A method of preventing liquid loss must be devised. In this case, it is desired that the liquid have a low viscosity so that it may easily flow into flaws; thus, raising the viscosity is not a satisfactory solution. One other inherent difficulty is caused by the high mobility of atoms in the liquid state as compared to the solid state. Because of this mobility, it would be expected that gases would diffuse more rapidly through a liquid. It is also probable that the solubility of oxygen in the liquid would be comparatively high. These factors would tend toward rapid permeation of oxygen and oxidation of the substrate. It is most reasonable that this problem could be solved by incorporating a solid phase, which is impermeable to gases, as a component of the coating. To overcome the tendency of a liquid to flow easily, it is possible to use surface tension to advantage. If the surface were made up of a large number of capillary tubes of sufficiently small diameter, then surface tension would hold the liquid even against the acceleration of a centrifugal field.

Jan 1, 1961