Search Documents

By J. H. Nead

The subject of this paper is one to which there are many references in the literature on the manufacture of steel in the open-hearth furnace, but few actual experimental data have been published. For that reason, the presentation of results obtained from two open-hearth heats where attempts were made to measure the sulfur absorption will be of considerable interest and value. The two heats on which the experiments were made were Armco ingot-iron heats and differ from the usual open-hearth heat of medium- or mild-carbon steel in that the refining is carried further; in this product the carbon and manganese are reduced practically to traces. In most other respects, and especially in respect to the absorption of sulfur from the producer gas, the two heats are typical of usual open-hearth practice. The object of the experiments made on the first Armco iron heat was to determine the fluctuation of the composition of the metal bath and the slag throughout the course of the heat, with especial reference to the variations in sulfur. It was hoped to determine whether there was an increase in sulfur in the bath from the producer gas and if so at what stage in the process the increase occurred. The experimental method consisted of charging analyzed scrap and pig iron, so that the sulfur in the charge could be calculated. Then, throughout the duration of the heat, metal and slag samples were takcn every half hour, beginning as soon as there was enough molten metal to take a sample. These samples were analyzed; the results are given in Table 1. All domestic scrap was used and the charge was made up as follows: Head End Finish Pounds Pound Pig iron........................ 36,300 Pig iron....................... 23,900 Sheet scrap bundles............. 36,200 Sheet bars..................... 23,900 Sheet bm..................... 40;200 The total charge, exclusive of the re-pig added near the end of the heat, was 160,500 Ib. The limestone charged was 21,400 Ib., or 13½ per cent.

Jan 1, 1924

Jan 1, 1927

Jan 1, 1947

Jan 1, 1947

Jan 1, 1938

Jan 1, 1938

Jan 1, 1943

Jan 1, 1943

Jan 1, 1958

Jan 1, 1911

Jan 1, 1953

Jan 1, 1938

Jan 1, 1938

By P. R. Celmer, Leonard R. Weisberg

THE principle of fractional crystallization has been successfully used to prepare high-purity (99.999 pct) Ga. Hoffman and Scribnerl removed single crystals of gallium solidifying in a gallium melt, while Zimmerman2 grew single crystals from the melt by the Kyropolous technique. In contrast, attempts at purifying gallium by zone refining have been less successful. ichards, reported that despite the passage of 40 zones through a gallium ingot, there still remained 5 to 70 ppm each of Cu, Fe, Ca, Mg, Si, Al, and Ag. Previously, Detwiler and Fox4 detected only one impurity, Pb, segregating in zone-refined ingots. These surprising results prompted an investigation of the factors controlling impurity segregation in gallium. Possible reasons for this were insufficient diffusion of impurities in the melt; recontamination of the melt by its oxide film which is not affected by the passage of the zone; reaction of gallium with the boat; sudden freezing of gallium following supercooling, especially since gallium easily supercools to and trapping of impurities at grain boundaries. Impurity segregation tests were carried out by directionally freezing gallium using the Bridgman rnethd, modified in that the molten gallium is lowered out of a furnace into a slush of dry ice and trichloroethylene, thus minimizing supercooling. Since the gallium is contained vertically, the oxide film is in contact only with the tail end of the melt. It was found that Teflon makes an excellent crucible for gallium since it is quite pure, non-reactive, translucent, flexible, machinable, and is not wet by gallium. The gallium crystals could be grown at various speeds, and the melt could be vigorously stirred by a Teflon rod moving through the gallium in a vertical reciprocating fashion. Single crystals could be grown by placing a solid Teflon plug at the bottom of the melt drilled out in such a way to cause the solidifying gallium to follow a winding path. Thus, even if many crystals are originally nucleated, only one grain will predominate. The grain structure of the gallium crystals was revealed by an etchant composed of equal volumes of HC1, HNO3 and HF, diluted with water to half strength. Emission spectrographic analyses were carried out on samples removed from the front and tail ends of the resulting gallium ingots. Typical results of this study are summarized in Table I. The rate of freezing in all three cases was about 1 in. per hr. It can be seen that even though stirring of the melt does help, it is even more important to grow a single crystal of Ga in order to obtain good segregation of impurities. The effect of crys-tallinity on the segregation of impurities was previously observed6 in the directional freezing of germanium; however, in this case, the effect was much less pronounced. This dependence of impurity segregation on the crystalline perfection of Ga may be related to its thermal conductivity which is the most anisotropic of all metals.7 The anisotropic thermal conductivity can cause the solid-liquid interface to be nonuniform, thus leading to trapping of impurities during freeing, and therefore reduced segregation. In conclusion, it is indicated that zone refining of gallium would be more successful if seeding and similar precautions are taken to insure single crystal growth. The authors are indebted to Mr. H. H. Whitaker for the spectrographic analyses and to Drs. B. Abeles and F. D. Rosi for helpful advice and encouragement throughout the course of this work. This research was supported by the Electronics Research Directorate, Air Research and Development Command, under Contract No. AF33(616)-5029. REFERENCES 'J. 1. IToffmon and B. T. Scribrer: I. Research h'atl. Bur. Standards, 1935, "01. 15, p. 205. 'W. Zirnmerman: Science, 1954, vol. 119, p. 41. %J. L. Richards: Nature, 1956, vol. 117, p. 182. 'D. P. Detwiler and W. M. Fox: I. Metals, 1955, "01. 7, p. 205. 5P. W. Bridgman, Proc. Am. ilcod. Sci., 1925, vul. 60, pp. 305,385,423. "S. L1. Christian: private c ommuni cation. 'K. W. Powell: roy. Sac., 1951, vol. 209, p. 525. 'W. G. Pfann: Zone Re fining, p. 20. John Wiley and Sons, Inc., New York, L058.

Jan 1, 1962

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

Congress has authorized the President to control the supply and distribution of the following: Antimony, arsenic, ball clay, bismuth, bromine, cerium, chalk, chromium, cobalt, corundum, emery, fluorspar, ferrosilicon, fullers' earth, graphite, grinding pebbles, iridium, kaolin, magnesite, manganese, mercury, mica, molybdenum, osmium, sodium, platinum, palladium, paper clay, phosphorus, potassium, pyrites, radium,

Jan 12, 1918

ASSETS Working Fund Assets Cash-unappropriated $62,41294 Members' 1951 dues receivable 14,336 98 Accounts receivable Advertising, publications and miscellaneous $43,22055 Less-Reserve for delinquent accounts 12,775 76 $30,44479 Petroleum Branch-Special Projects Fund¬ Advances re Petroleum Conservation Volume 5,37085 35,81564

Jan 1, 1952

(Under this heading will be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Member, aged 34, married, technical graduate, 10 years' experience as mining engineer and mine superintendent, desires position. Can show low cost records and good references. No. 176.

Jan 1, 1916

By M. Oka, C. M. Wayman

It has been known for some time1 that (110)b twinning is possible in bct martensite.* Any plane of the form (110) not parallel to the fourfold axis of tetra-

Jan 1, 1969

United Engineering Trustees, Inc Engineering Foundation Engineering Societies Research Board Other Committees United Engineering Trustees, Inc. ARTHUR S. DWIGHT GEORGE D. BARRON J. V. N. DOER Engineering Societies Library Board ROBERT PEELS PHILIP W. HENRY GEORGE C. STONE JOSEPH E. POGUE The Engineering Foundation H. C. BELLINGER GALEN H. CLEVENGER J. V. N. DORR

Jan 1, 1929