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By A. R. Orban, R. B. Engdahl, J. D. Hummell

The initial phase of a research program on smoke abatement from Bessemer converters is described. In work sponsored by the American Iron and Steel Institute, a 300-lb experimental Bessemer converter was assembled to simulate blowing conditions in a commercial vessel. Measurements of smoke and dust were also made in the field on a 30-ton commercial vessel. During normal blows the dust loading from the laboratory converter averaged 0.51 lb per 1000 lb of exhaust gas. This was similar to the exhaust-gas loading of a commercial vessel. The addition of hydrogen to the blast gas of the laboratory converter caused a decided decrease in smoke density. Smoke was also reduced markedly when methane or ammonia was added instead of hydrogen. The research is continuing on a bench-scale investigation of the mechanism of smoke formation in the converter process. DURING the past 2 years, on behalf of the American Iron and Steel Institute, Battelle has been conducting a research program on the control of emissions from pneumatic steelmaking processes. The objective of the research program is to discover a practical method for reducing to an unobjectionable level the emission of smoke and dust from Bessemer converters. PRELIMINARY INVESTIGATION Although conceivably some new collecting technique may be devised which would be economically practicable for cleaning Bessemer gases, no such system based on presently known principles seems feasible because of the extremely large volume of high-temperature gases involved. Hence, the research is being directed toward prevention of smoke formation at the source. A thorough review was first made of former work to determine the present status of the cleaning of converter gases. No published work was found on work done in the United States on collecting smoke or on preventing its formation in the bottom-blown, acid-Bessemer converter. In Europe, however, a number of investigations have been made on the basic-Bessemer converter. Kosmider, Neuhaus, and Kratzenstein1 conducted tests on a 20-ton converter to obtain characteristic data for dust removal and the utilization of waste heat. They concluded that because of the submicron size of the dust, special equipment would be necessary to clean the exhaust gases. Dehne2 conducted a large number of smoke-abatement experiments at Duisburg-Huckingen in a 36-ton Thomas converter discharging into a stack. A number of wet-scrubbing and dry collectors were tried unsuccessfully. A waste-heat boiler and electrostatic collector with necessary gas precleaners was felt to be the best solution for this particular plant. Meldau and Laufhutte3 determined that the particle size was all below 1 µ in the waste gas of a bottom-blown converter. Sel'kin and zadalya4 describe the use of oxygen-water mixtures injected into a molten bath in refining open-hearth steel. They claim that with use of oxygen-water mixtures the amount of dust formed was reduced between 33.3 and 20 pct of its previous level, and emission of brown smoke almost ceased. Pepperhoff and passov5 attempted unsuccessfully to find some correlation between the optical absorption of the smoke, the flame emission, and the composition of the metal in a Thomas converter in order to determine automatically the metallurgical state in the melt. In a recent U. S. Patent (NO. 2,831,762)' issued to two Austrian inventors, Kemmetmuller and Rinesch, the inventors claim a process for treating the exhaust gases from a converter. By their method the inventors claim that the exhaust gases from the converter are cooled immediately after leaving the converter to a degree that oxidation of the metal vapors and metal particles to form Fe2O3 is inhibited in the presence of surplus oxygen. Gledhill, Carnall, and sargent7 report on cleaning the gases from oxygen lancing of pig iron in the ladle. They claim the Pease-Anthony Venturi scrubber removed 99.5 + pct of the smoke, thereby reducing the concentration to 0.1 to 0.2 grain per cu ft, which resulted in a colorless stack gas after the evaporation of water. Fischer and wahlster8 developed a small basic converter and compared the metallurgical behavior of the blow with that of a large converter. Later work by Kosmider, Neuhaus, and Hardt9 on the use of steam for reduction of smoke from an oxygen-enriched converter confirmed that the cooling effect of steam is detrimental to production. From review of all of the published information on the subject, it was concluded that a practical solution to the smoke-elimination problem had not been found. Accordingly, it was deemed desirable to investigate the feasibility of preventing the initial formation of smoke in the converter.

Jan 1, 1961

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

By W. Hume-Rothery

IN recent interesting papers,1,2 Bardos et al. have described ternary Laves phases of the type A2(BsSi) and A4(B5Si3) where A = titanium vanadium, niobium, and so forth, and B = manganese, iron, cobalt, or nickel; other more complex formulae have also been established. In these phases, silicon plays the part of the smaller B atom of a Laves phase AB2, and the interatomic distances show that the effec- tive silicon radii lie between 1.16 and 1.21Å, and are thus very much smaller than the metallic radius of silicon for CN = 12. It does not seem to have been pointed out that these small atomic radii are almost the sape as the normal covalent radius of silicon (1.174Å). If, therefore, silicon acts as an acceptor of electrons as suggested by Bardos et al.,1 it appears to do so, not by the building up of a negatively charged silicon ion which would be large, but by the formation of what are very nearly or may be actually normal covalent bonds. Since a covalent bond contains two electrons, its formation would reduce the number of electrons available for bonding in other parts of the structure, and in this way the effect of silicon in stabilizing the o phase at high electron concentrations might be understood.

Jan 1, 1965

By Carl E. Johnson

INTRODUCTION A method for predicting water-flood oil recovery was reported by H. Dykstra and R. L. Parsons' in 1950. It is now generally known as the Dykstra-Parsons method and is widely used by petroleum engineers. The method is semiempirical and consists of a correlation of four fundamental variables. These are: V, vertical permeability variation;' a, mobility ratio; Sw initial water saturation; and R, fractional recovery of oil in place at a given producing water-oil ratio. The correlation extends over a wide range in each of these variables, and may be applied to all formations with initial oil saturations of 45 per cent or greater. The method of calculation originally outlined by Dyhtra and Parsons closely follows their derivation. And this is a convenient way of illustrating the development of some rather complicated ideas. However, in actual use it is more cumbersome than necessary. The purpose of this note, therefore, is to provide a simplified method for making Dykstra-Parsons predictions. A SIMPLIFIED GRAPHICAL SOLUTION The correlation between V, a, Sw and R, corresponding to a given producing water-oil ratio, can be shown on a single graph. This is best done by plotting V against a to show lines of constant R(1 - S, . WOR-0.2). Figs. 1, 2, 3, and 4 show these plots

Jan 1, 1957

By R. W. Raymond

The important question of the metallurgical value of the coals of the Rocky Mountains and the Pacific Coast is to be settled, of course, by practical experiment. Meanwhile, as I have had occasion to point out, the proximate analyses of these coals throws little light upon it, and is, indeed, likely to mislead the metallurgist, if he compares it with the results of similar analyses upon bituminous and semi-bituminous coals. With the view of showing how large a proportion of the material usually classed as(" volatile matters " consists of combined water, or oxygen and hydrogen presumably in chemical combination, I have collected a number of ultimate analyses from various sources, in the following tables. The numbered analyses in the first table are as follows: No. 1. Monte Diabolo coal—Analyst, H. S. Munroe, Col. School of Mines. 2. Weber Canon, Utah, " " " 3. Echo Canon, " " " " 4. Carbon Stat'n, Wyoming, " " " 5. " " " " " 6. Coos Bay, Oregon, " " " 7. Alaska, " " " 8. " " " " 9. Canon City, Colorado, " Dr. T. M. Drown, Philadelphia. 10. Baker Co., Oregon, " " " 11. Blockcoal,SandCr'k,Ind., " Prof. E. T. Cox. This table affords some suggestive comparisons, to facilitate which a remark or two, explanatory of its construction, will be useful. In the ultimate analysis of coals, the proportions are frequently calculated (as, for instance, in the report for 1872 of Prof. Cox, State

By B. C. Craft, T. J. Johnson, H. L. Kirkpatrick

Petroleum engineers are displaying considerable interest in the problems of cementing oil wells, especially in the Gulf Coast and California areas, where steep temperature gradients are encountered and where wells are being drilled to greater depths. Deep drilling, that is, at depths in excess of 7000 ft., has been undertaken in these areas only in the last few years and with this trend oil-well cementing requires more technical treatment. It is not the purpose of this paper to describe the scope and application of cement operations in the oil industry or to give the standard specifications, methods of sampling and testing of portland cement. The various testing methods have been described by the American Society for Testing Materials1, Uren2, Tickell and Wankowski3 and Rakestraw and Parsons4. The latter authors (pp. 50-58) have also described in detail the methods of cementing. The authors realize that it is impossible to reproduce in the laboratory the scale of forces and dimensions that exist at great depths, but an attempt has been made to scale down these dimensions proportionally. The selection of problems to be studied was based largely upon the practical questions asked by several of the largest operators in these fields. All cements used in these experiments met the specifications of the American Society for Testing Materials.

Jan 1, 1935

By Fritz Wald, Richard W. Stormont

lHE general constitution of a number of metal-lead telluride and metal-tin telluride systems has recently been studied in an effort designed to furnish background information for the study of degradation mechanisms on junctions between thermoelectric power generation materials and metals.1"4 This paper reports further results of that effort. It was found that cobalt-lead telluride constitutes a stable pseudobinary section through the ternary Co-Pb-Te system. Materials used in the study were lead and tellurium of semiconductor-grade purity (American Smelting and Refining Corp., 99.999+ pet). Cobalt (Johnson Matthey & Co., 99.999 pet purity) was used in the form of slices cut from rods of 5 mm diam. Twenty- gram charges of the alloys were melted in evacuated quartz ampoules. Thermal analysis, as described previously,2'3 and metallographic and X-ray diffraction methods (Debye-Scherrer photographs) were used as investigative tools. Substantial difficulties were encountered in polishing, as reported previously for the lead telluride-iron system.3 A number of different etches were used, including dilute aqua regia, Murakami solution, an etch containing copper nitrate,3 and HC1-HNO3-acetic acid-water mixtures. None of these etches gave consistent results over the complete range of cobalt concentrations. On the alloys containing bulk cobalt in the form of primary

Jan 1, 1969

By R. V. Lundquist

R. T. Hukki (Finland Institute of Technology, Helsinki, Finland)—Two schools of thought are developing concerning the order of the rate of flotation. The paper by Morris is intended to show experimental evidence in favor of the first order rate. Arbiter, on the other hand, has presented an earlier paper" to demonstrate the validity of the second order rate equation. Unfortunately his method of plotting is open to criticism, as pointed out by Morris." A more sensitive method of plotting has been described by the writer,= whereby the data presented by Arbiter demonstrate the superiority of the second order plot. The general rate equation may be written in the following forms for the integrated first and second order equations: (A) t =------In—-------- (first order) [4] 1 1 (B) — = — kc, + KC°²— (second order) [5] t R As a first approximation the value of C, may be taken as a unity, 100 pct or 1. Whether or not this is the case in all tests performed by Morris is impossible to judge, owing to the fact that the flotation times are extremely short, e.g. 150 sec in tests A. It would, indeed, be very interesting to know what the total recovery R would be after 1 hr of flotation, for example, instead of after 150 sec. Certainly there are circumstances when C, approaches unity within a very small

Jan 1, 1954

By C. W. Spencer, B. F. Addis, G. H. Bishop, C. A. Steidel

STUDIES of the inter granular attack of metals by liquids have generally been confined to polycrys-talline specimens. This note reports the results of preliminary studies of the penetration of bismuth-rich Ni-Bi liquids into oriented bicrystal specimens of nickel. It is found that isothermal penetration follows a parabolic rate law and shows a definite anisatropy with respect to direction on the grain boundary surface. Nickel bicrystals containing < 100> tilt boundaries were grown using the Czochralski method. Relative misorientation of the parent crystals was controlled to ± 1deg. The boundaries are straight in the growth direction, i.e., the common <100>, and generally straight in the transverse direction, as shown in Fig. 1. The starting material, Inco HPM grade nickel was contained in a recrystallized alumina crucible and maintained under argon. Bicrystals typically contain 30 ppm C, less than 10 ppm S, O, N, and 50 ppm residual metallics, principally iron and silicon. Specimens, as schematically illustrated in Fig. l(c),were cut from bicrystal ingots using a thin water-cooled abrasive wheel. To insure removal of all residual strain, which accelerates the penetration, specimens were round through 600 grit silicon-carbide, chemically polished, and annealed for 4 hr at 1375°C under argon. The procedure described by Cheney et al.1 for exposing specimens to

Jan 1, 1962

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S,), is ground with sodium or potassium hydroxide, the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture.

Aug 1, 1956

By W. C. Smith, P. J. Hickey

After a short historical background of the process evolution, this article descvibes present-day plant facilities and operating techniques utilized for high-purity bismuth production. The plant is one of the world&apos;s largest, with an annual output of some one million pounds of refined bismutlz. PREVIOUS papers1 written by staff members of Cerro de Pasco Corp. have referred briefly to the production of refined bismuth. Since the Corporation is one of the world&apos;s foremost producers of high-purity bismuth, a detailed description of the process for extracting the metal may be of general interest. Following a short historical background of the development of the actual process, this presentation will trace the progress of bismuth from its entry into the primary smelting circuits to its concentration in electrolytic lead cell slimes. Our facilities for the treatment of anode muds will be described and the extractive methods given in some detail, with particular emphasis on the techniques which result in the production of refined metal. HISTORICAL BACKGROUND Shortly after Cerro de Pasco began smelting operations at Oroya, Peru in 1922, it became apparent that the dust carried by copper converter gas contained appreciable amounts of bismuth. Although dust collection efficiency was poor prior to building of the 550-ft stack and installation of the central cottrells in 1938, a large stock of dust was accumulated during the intervening years, having the following approximate composition: Oz. per ton Ag - 11.0 Pct Sn — 0.5 Pct Pb - 49.0 Pct Zn - 6.5 Pct Bi - 2.0 Pct Insol. - 1.5 Pct Cu - 0.7 Pct Fe - 2.3 Pct Sb - 3.0 Pct S - 10.0 Pct As - 7.5 In the mid-1920&apos;s, experimental crucible melts of this dust with carbon indicated that most of the bismuth and silver, and some of the lead, could be reduced to a fairly clean bullion. Other products were a small amount of leady copper matte and a slag high in zinc, arsenic, antimony, and lead; this slag contained some tin but only small quantities of silver, bismuth, and copper. After the laboratory results had been confirmed by operation of a small reverberatory, a dust reduction furnace was constructed. The ±10 pct Bi-Pb bullion produced from this operation was stocked until 1930, when an Oroya-designed converter type furnace3 was installed for the elimination of arsenic, antimony, and some lead from the bullion. This process concentrated the bismuth from 10 to about 60 pct. By means of the bismuth process developed4 by W. C. Smith at East Chicago (1909-1914) and the discovery of a method5 for separation of lead from bismuth with chlorine gas in 1929, it became possible to begin production of refined bismuth. Unfortunately, bismuth deleaded with chlorine always contained residual chlorides, and the removal of the chlorides by caustic soda left a lead content of 0.02 to 0.04 pct. This final problem was solved6 by substitution of air-blowing for the caustic treatment, which effectively removed all excess chlorine and gave bismuth which was practically lead-free. In 1934, a pilot electrolytic lead refinery began operations at Oroya. Lead smelting was resumed in 1935 and two years later a 100-ton-per-day lead refinery was put into service. In conjunction with the latter, the present-day Anode Residue Plant was constructed. Until 1940, the plant treated both lead anode slimes and dust reduction bullion. The dust reduction furnace was shut down in that year, and all cottrell dusts (with the exception of the product from the arsenic cottrell) were mixed with pyrite and treated in a Wedge roaster to eliminate all possible arsenic. Calcine from this operation joined the sinter plant feed; hence the bismuth from the copper and lead circuits was collected in the lead bullion and subsequently in lead anode slimes from the electrolytic lead refinery. The latter source has been the only bismuth-bearing material of any consequence entering the Anode Residue Plant from late 1940 to the present. A copper refinery began operating in 1948, and the cell mud from this plant is mixed with lead slimes and processed through the same circuit, though only a small quantity of bismuth is present in electrolytic copper cell residues. BISMUTH INTAKE Present-day routes which are followed by the new bismuth feed from its entry into the primary smelting circuits to its arrival at the Anode Residue Plant are traced schematically in Fig. 1. As illus-

Jan 1, 1962

Jan 1, 1920

By H. J. Ramey

The wellbore acts as a storage tank during drawdown and build-up testing and causes the sand-face flow rate to approach the constant surface flow rate as a function of time. This effect is compounded if non-Darcy flow (turbulent flow) exists near a gas wellbore. Non-Darcy flow can be interpreted as a flow-rate dependent skin effect. A method for determining the non-Darcy flow constant using this concept and the usual skin effect equation is described. Field tests of this method have identified several cases where non-Darcy flow was severe enough that gas wells in a fractured region appeared to be moderately damaged. The combination of wellbore storage and non-Darcy flow can result in erroneous estimates of formation flow capacity for short-time gas well tests. Fortunately, the presence of the wellbore storage eflect permits a new analysis which can provide a reasonable estimate of formation flow capacity and the non-Darcy flow constant from a single short-time test. The basis of the Gladfelter, Tracy and Wilsey correction for wellbore storage in pressure build-up was investigated. Results led to extension of the method to drawdown testing. If non-Darcy flow is not important, the method can be used to correct short-time gas well drawdown or build-up data. A method for estimation of the duration of wellbore storage effects was developed. INTRODUCTION In 1953, van Everdingen and Hurst generalized results published in their previous paper3 concerning wellbore storage effects to include a "skin effect", or a region of altered permeability adjacent to the wellbore. Later, Gladfelter. Tracy and Wilsey4 presented a method for correcting observed oilwell pressure build-up data for wellbore storage in the presence of a skin effect. The method depended upon measuring the change in the fluid storage in the wellbore by measuring the rise in liquid level. To the author&apos;s knowledge, application of the Gladfelter, Tracy and Wilsey storage correction to gas-well build-up has not been discussed in the literature. It is, however, a rather obvious application. Gas storage in the wellbore is a conlpressibility effect and can be estimated easily from the measured wellbore pressure as a function of time. Several approaches to the wellbore storage problem have been suggested. As summarized by Matthews, it is possible to minimize annulus storage volume by using a packer, and to obtain a near sand-face shut-in by use of down-hole tubing plug devices. Matthews and Perrine have suggested criteiia for determining the time when storage effects become negligible. In 1962, Swift and Kiel&apos; presented a method for determination of the effect of non-Darcy flow (often called turbulent flow) upon gas-well behavior. This paper provided a theoretical basis for peculiar gas-well behavior described previously by Smith. Recently, Carter, Miller and Riley observed disagreement among flow capacity k,,h data determined from gas-well drawdown tests conducted at different flow rates for short periods of time (less than six hours flowing time). In the original preprint of their paper, Carter et al. proposed that the discrepancy in flow capacity was possibly a result of wellbore storage effects. Results of an analytical study of unloading of the wellbore and non-Darcy flow were recorded by carter.14 In the final text of their paper, Carter et al.!&apos; stated that they no longer believed wellbore storage was the reason for discrepancy in their kgh estimates. In view of the preceding, this study was performed to establish the importance of non-Darcy flow and well-bore storage for gas-well testing. In the course of the study. a reinspection of the previous work by van Everdingen&apos; and Hurst&apos; was made, and the basis for the Gladfelter, Tracy and Wilsey&apos; wellbore storage correction was investigated and extended to flow testing. WELLBORE STORAGE THEORY As has been shown by Aronofsky and Jenkins,11-12 Matthews," and others, flow of gas can often be approximated by an equivalent liquid flow system. The following developnlent will use liquid flow nomenclature to simplify the presentation. Application to gas-well cases will be illustrated later. First, we will use the van Everdingen-HursP treatment of wellbore storage in transient flow to establish (1) the duration of wellbore storage effects, and (2) a method to correct flow data for wellbore storage. DURATION OF WELLHORE STORAGE EFFECTS When an oil well is opened to flow. the bottom-hole pressure drops and causes a resulting drop in the liquid level in the annulus. If V. represents the annular volume in cu ft/ft of depth, and p represents the average density of the fluid in the wellbore, the volume of fluid at reservoir conditions produced from the annulus per unit bottom-hole pressure drop is approximately: res bbl-- (V, cu ft/ft) (144 sqin./sq ft) psi -(5.615 cu ft/bbl)(pIb/cuft) ........(I)

Jan 1, 1966

By John Wulff, David A. Stevenson

The solubility of iron and cobalt in liquid lead, the solubility of chromium in liquid tin, and nickel in liquid silver were determined up to 1300°C in an atmosphere of hydrogen. Liquid samples were taken at different temperatures and analyzed. The data obtained were plotted to show the relationship between log mole fraction of solute and the inverse of the absolute temperature. Resulting values for the differential heat of solution (AH) and the excesspartial molar entropy (S)are: for the iron-lead system = _24,200 cal per mole and AT = 5.0 e.u. for the a phase, and AH = 18,300 and S = -0.1 e.u. for the y phase; for the cobalt-lead system AH = 16,500 cal per mole and AS =0.7 e.u.; for the chromium-tin system AH = 15,600 cal per mole and AS = 8.5 e.u.; for the nickel-silver system AH =18,000 cal per mole and AS = 4.0 e.u. RECENT developments in coating, brazing, and heat transfer have focused attention on specific cases of solid-liquid interaction in metal systems, particularly those involving dilute liquid solutions. One fundamental quantity of interest in such systems is the equilibrium phase distribution between solid and liquid phases. In any effort to fully understand such interactions, one must be able to describe the equilibrium state precisely. Furthermore, in order to develop genera! relations for such systems, one must know the equilibrium state in a number of different cases. This investigation was devoted to a study of the equilibrium phase distribution in four binary systems: solid iron-liquid lead; solid cobalt-liquid lead; solid chromium-liquid tin; solid nickel-liquid silver. The iron-lead system was previously studied by Shepard and parkman&apos; and later by Fleischer and Elliott2 with differing results. Both investigations were carried out by sampling the saturated liquid, and analyzing it chemically. The cobalt-lead system was previously reported by Pelzel,3 who noticed no discontinuity near the transformation. A limited investigation of the chromium-tin system was made by Wlodek and wulff4 using a weight loss method. This work was done in conjunction with the development of a process for coating molybdenum with chromium from tin solutions. To more fully under- stand the kinetics of the process, a more accurate determination of a solubility was desirable. No significant data were found in the literature on the nickel-silver system. Data on the latter system were, however, relevant to the investigation of the corrosion kinetics of copper-nickel alloys in liquid silver as carried out by Harrison and wagner,5 EXPERIMENTAL APPARATUS AND PROCEDURE Of the techniques available for the study of such systems the most effective appears to be that of liquid sampling,2,6,7 which is the method used in the present investigation. A schematic diagram of the sampling furnace is given in Fig. 1. Large pieces of solute metal, in excess of saturation solubility, were added to 200 g of the solvent metal, and the entire charge placed in an alundum crucible. Analytical reagent or materials of chemically pure grade were used in all investigations. The crucible was contained in a zircon muffle tube positioned vertically in the uniform hot zone of a Globar resistance furnace. The tube was provided with a number of ports which permitted sampling at temperature and in controlled atmospheres or vacuum; the ports were also useful for evacuation and introduction of gases as well as for thermocouple measurements. A chromel-alumel thermocouple Sheated in a porcelain tube was used for temperature measurements. A purified hydrogen atmosphere was employed in all experiments reported in this paper. The hydrogen was purified by passing it first over hot copper gauze to remove oxygen and then through a molecular sieve immersed in

Jan 1, 1962

By Norman F. Schulz, Emert W. Lindroos, Strathmore R. B. Cooke

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous &apos;60 per cent&apos; alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous &apos;60 per cent&apos; alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

IT is a pleasure for the translators to record their gratitude to the Seeley W. Mudd Memorial Fund of the American Institute of Mining and Metallurgical Engineers for underwriting the cost of publication of this volume, to the Printing-Office of the Yale University Press for doing an unusually fine printing job, and to the following for granting permission to reproduce the title pages of volumes in their collection: The Bibliothèque Nationale of Paris, for edition A of the Bergbüchlein; the Osler Library of McGill University, Montreal, for editions B and G of the Bergbüchlein and edition D of the Probierbüchlein; Mr. Herbert Hoover, Jr., for editions C and E of the Bergbüchlein and editions E, M, N, and 0 of the Probierbüchlein; the Parsons Collection of the Reference Department of The New York Public Library, for edition D of the Bergbüchlein; the Library of the Bergakademie Freiberg, for edition F of the Bergbüchlein and editions A, H, and L of the Probierbüchlein; the Herzog August-Bibliothek of Wolfenbüttel, for edition C of the Probierbüchlein; the British Museum. Library, London, for edition I of the Probierbüchlein; and the library of the University of California at Berkeley, for edition J of the Probierbüchlein. The cooperation of those who helped with the translation of the Bergbüchlein is acknowledged on p. 64. A. G. S. C. S. S.

Jan 1, 1949

By Albert E. Wood, Edgar R Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as &apos;&apos;308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By Albert E. Wood, Edgar R. Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as &apos;&apos;308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By I. Fatt

A recently developed system for measuring electrical resistivity of liquids without use of electrodes offers some interesting possibilities in electric logging technology. The equipment as supplied by the manufacturer is satisfactory for continuous mud logging on a drilling rig or for measuring mud or filtrate resistivity in the laboratory. A simple modification of the commercially available instrument makes it suitable for measuring resistivity of core samples in the laboratory. The continuous measurement of mud resistivity on a drilling rig is a convenient means for detecting mixing of formation water with the drilling mud. Such information is useful to the geologist, the mud engineer and the logging engineer. However, continuous mud resistivity logging by conventional electrode-type resistivity cells is beset with difficulties. The mud, sand and rock chips abrade the electrodes, thereby changing the cell constant and eventually destroying the cell. Also, additives and crude oil in the mud may poison the electrodes by coating them with a nonconductive material. An electrode-type resistivity cell. therefore, may give erroneous readings under certain conditions. Electric logging companies circumvent the electrode poisoning problem by using a four-electrode resistivity cell for measurement of mud resistivity. In this cell, change in electrode area does not change the cell constant. However, the four-electrode cell is difficult to adapt for continuous reading and does not solve completely the problem of electrode abrasion by the sand and cuttings in the mud. The measurement of electric logging parameters on core samples in the laboratory encounters some of the same problems discussed in connection with mud logging. Ideally, the electrical resistivity of a core sample should be measured by placing platinum black electrodes in direct contact with the plane ends of a cylindrical or rectangular sample. Platinum black electrodes however, are much too fragile and easily abraded to be brought in contact with a rock sample. Also, oil or other constituents in the fluid contained in the sample will poison platinum black. In practice, gold-plated brass electrodes, in an AC bridge circuit operating at about 1,000 cps, are used for routine core analysis. For more precise work in research studies, a four-electrode scheme is used.&apos;,&apos; Preparation of the samples for the four-electrode method is much too involved for routine core analysis. An apparatus for measuring resistivity of liquids without use of electrodes was described by Guthrie and Boys3 in 1879. They suspended a beaker, containing the electrolyte, by a torsion wire and rotated a set of permanent bar magnets around the vessel. The eddy currents induced in the electrolyte reacted against the rotating magnetic field to develop a torque, which was measured as a deflection of the torsion wire. In 1879 this method could not be made precise or convenient because of the lack of strong permanent magnets. The writer described a very greatly improved apparatus similar to that of Guthrie and Boys, but it was not suitable for continuous measurements or core samples.&apos; Many electrodeless resistivity devices using radio frequency current are described in the literature.5, 6 These generally are suitable only for noting the end-point in a chemical titration. They do not measure resistivity, instead measuring a complex quantity which includes the dielectric constant and the magnetic permeability. The first description of the apparatus to be discussed in this paper was given by Relis.7 Improvements and modifications are described by Fielden,s Gupta and Hills,> and Eichholz and Bettens.10 DESCRIPTION OF APPARATUS The apparatus used in this study is based on the principle that the solution under measurement can form a loop coupling two transformer coils, as shown in Fig. 1. For a fixed AC voltage applied across Coil A, the voltage appearing across Coil B is a function of the resistance of the liquid-filled loop. The details of the voltage generating and measuring circuits are given in Refs. 7, 8, 9 and 10. A block diagram of the equipment is given in Fig. 7. Special features worth mentioning are the operating frequency of 18,000 cps and the automatic temperature compensation which results in the given resistivity readings being automatically correlated to 25°C. The liquid loop supplied by the manufacturer, shown in Figs. 1 and 2, was modified for use in core analysis (Fig. 3). The core sample under test is substituted for a section of the original loop. As shown in Fig. 3, the unit accepts only plastic-mounted cylindrical core specimens. A Hassler-type sleeve easily can be designed for the unit if unmounted cores are to be measured. EXPERIMENTAL PROCEDURE MUD LOGGING A simulated mud line was set up in the laboratory.