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By Earl Bardwell

THE determination of suitable and safe annealing temperatures is one of the most important problems arising in the operation of a copper rolling mill. Certain of the larger mills have worked this problem out for themselves and in these mills the operation has become more or less standardized. In some of the mills pyrometers are used to measure the temperature of the annealing furnaces and careful watch is kept to see that overheating does not take place. In a considerable number of the mills, however, dependence is placed entirely on the judgment of the operator. The almost total lack of literature bearing on this subject seems sufficient warrant for the publication of this paper. The discussion of this subject naturally divides itself into two parts: (1) The effect of annealing temperature on physical properties; and (2) changes in the microstructure of refined copper due to cold rolling and annealing. I. THE EFFECT OF ANNEALING TEMPERATURE ON PHYSICAL PROPERTIES For the purpose of investigating this phase of the subject six test bars were selected, varying in oxygen content between the limits of 0.036 and 0.070 per cent. The chemical composition of each of these test bars was as follows:

Jan 8, 1914

[Aalde, Kaare, ('40) New Mexico School of Mines, Socorro, N. M. Abadesco, Enrique A., ('39) Univ. of the Philippines, Manila, P. I. Abdul-Ahad, A., ('39) Montana School of Mines, Residence Hall, Butte, Mont. Abreu, Ovidio M., ('38) Univ. of Nevada, Reno, Nev. Acker, Voscoe, . ('39) Agricultural & Mech. College of Texas, College Station, Tex. Acosta S., Gonzalo, ('40) Univ. of Texas, Univ. Sta., Box 1785, Austin, Tex. Adams, Albert, ('38) New Mexico School of Mines, Socorro, N. M. Adams, Charles W.,' ('39) Michigan College of Min. & Tech., Houghton, Mich. Adams, Hugh T., Jr., ('39) Univ. of Oklahoma, Norman, Okla. Adams, Jack L., ('39) Univ. of Oklahoma, Norman Okla.]

Jan 1, 1940

By H. H. Johnson, Eric W. Johnson

A newly developed ac technique was used to measure the electrical-resistivity changes associated with both cyclic stressing and subsequent annealing of high-purity and OFHC copper. The early stage of push-pull fatigue was explored at 293° and 4.2°K, with stresses chosen for an expected fatigue life of 2 to 8 X 105 cycles. For high-purity copper, fatigue at 293°K was accompanied by an initial increase in resistivity. After about 5000 stress cycles, no further increase was observed. Annealing studies showed that the resisticity increment could be accounted for solely in terms of an increased dislocation density, to about 2 x 1010 disl pev sq cm. Fov 42°K fatigue, however, the resistivity increased continually, with no evidence of saturation, as approximately (No. of stress cycles)1/4. This is intevpreted to result from both dislocation multiplication and vacancy production; estimated vacancy concentrations are 10-4 to 10-9. The continuous resistivity increase was inhibited by interspersed annealing treatments at 293°K, which also raised the level of the stress-strain curve. These effects are attributed to annealing of vacancies into dislocation loops. In contrast, OFHC copper fatigued at 4.2°K showed saturation of electrical vesistivity after only a few hundred cycles, and it appeared that vacancies annealed out completely between 77° and 293°K. MaNY observations suggest that both dislocation multiplication and point-defect production are important aspects of fatigue deformation. An increase in dislocation density with number of stress cycles has been demonstrated or implied by several experimental techniques, including optical metallography with lithium fluoride,' electron microscopy with copper,2 thermal conductivity of Cu-Zn alloys,3 and peak-stress measurements during cycling at constant plastic strain amplitude.4,5 At low amplitudes and/or stresses saturation of fatigue hardening and dislocation density occurs early in the expected fatigue life,4-6 frequently by a few hundred cycles. The evidence for point-defect production is somewhat less extensive, but it is nonetheless persuasive. Rosenberg7 reported briefly that, for equal stresses, copper fatigued at liquid-hydrogen temperature displays an increase in electrical resistance some ten times that which accompanies unidirectional stressing. Further, the extra resistance saturates after a few hundred stress cycles, and does not anneal significantly until a temperature of about 170°K is attained.' Point-defect production during fatigue is also suggested by 1) the softening during cyclic stressing of initially strain-hardened polycrystal-line copper9, 2) the strong temperature dependence of the yield strength of fatigue-hardened mono- and polycrystalline copper,579"0 and 3) the influence of intermediate annealing upon slip-band formation in copper fatigued at 90°K.8 It is evident that characterization of the fatigued state requires a knowledge of both point-defect and dislocation densities. For this purpose electrical-resistivity measurements are useful, but they are difficult to perform because of geometric limitations. Push-pull fatigue is necessary to obtain a macroscopic ally uniform deformation over the specimen cross section; however, the specimen must then have a low slenderness ratio to avoid plastic buckling, while the standard dc resistivity technique requires a very slender specimen for

Jan 1, 1965

By James M. Barker

Sulfur is a nonmetallic element of great physical and economic importance to the world. It is widely but sparingly distributed throughout the hydrosphere, lithosphere, and biosphere. Sulfur is the tenth most abundant element in the universe and eighth most abundant in the sun. In the earth's crust, which is mainly igneous, it ranks 14th, but is eighth or ninth in sediments (Kaplan, 1972; Stanton, 1972). It apparently is very abundant in the core of the earth, because it is a strong chalcophile, and it is fifth in abundance in stony and iron meteorites (Field, 1972) where it occurs as trolite (FeS). In ancient times sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Shelton (1979) summarized most of the common definitions of terms, grades, and specifications for the sulfur industry as follows (with minor additions): Sources of Sulfur: Combined sulfur-Sulfur that occurs in nature combined with other elements. Cupriferous pyrites-Pyrite containing relatively minor amounts of copper sulfide minerals. Hydrogen sulfide-A toxic gas (H2S) occurring in natural gas and petroleum. Involuntary sulfur-Sulfur produced primarily as a result of legislative or process mandates. Native sulfur-Sulfur that occurs in nature in the elemental (uncombined) form. Nonferrous metal sulfides-Copper, lead, zinc, nickel, and molybdenum sulfides that are processed for their metal content. Organic sulfurs-Complex organic sulfur compounds occurring in petroleum, coal, oil shale, and tar sands. Pyrites-Iron sulfide minerals that include pyrite, marcasite, and pyrrhotite. Sulfate sulfurs-Sulfur in anhydrite and gypsum. Voluntary sulfur-Sulfur produced in response to market forces. Basic Sulfur Products Produced and Marketed: Acid sludge-Contaminated sulfuric acid usually returned to acid plants for reconstitution. Brimstone-Synonymous with crude sulfur. Bright sulfur-Crude sulfur free of discoloring impurities and bright yellow in color. Broken sulfur-Solid crude sulfur crushed to -8 in. Byproduct sulfuric acid--Sulfuric acid produced as a byproduct of a metallurgical or industrial process, generally relating to combined sulfur sources. Crude sulfur-Commercial nomenclature for elemental sulfur. Dark sulfur-Crude sulfur discolored by minor quantities of hydrocarbons ranging up to 0.3 % carbon content. Elemental sulfur-Processed sulfur in the elemental form produced from native sulfur or combined sulfur sources, generally with a minimum sulfur content of 99.5%. Formed sulfur-Elemental sulfur cast or pressed into particular shapes to enhance handling and to suppress dust generation and moisture retention. Frasch sulfur-Elemental sulfur produced from native sulfur sources by the Frasch mining process. Hydrogen sulfide-Associated with natural gas or petroleum and produced at refineries and coke oven plants; used to make sulfuric acid or recovered sulfur. Liquid sulfur-Synonymous with molten sulfur. Liquid sulfur dioxide-Purified sulfur dioxide compressed to the liquid phase. Molten sulfur-Crude sulfur in the molten phase.

Jan 1, 1983

CONTENTS PAGE Need for Research in Foundry Pig Iron. By Richard Moldenke. (With Discussion) 1 Carbon Characteristics of Copper-bearing Pig Iron. By W. B. Coleman. (With Discussion) 12 A Pig Iron, Low in Total Carbon, is in Demand for Use in Various Industries. By Enrique Touceda. (With Discussion) 24 Carbon in Pig Iron. By Ralph H. Sweetser. (With Discussion) 28 Second Session (Discussion) 37 Need for Research in Foundry Pig Iron BY RICHARD MOLDENKE,* WATCHUNG, N. J. So FAR as the quality of the product is concerned, the history of the production of pig iron for foundry purposes is one of constant retrogression. The steps in this deterioration began with cold-blast charcoal pig iron, then anthracite iron, coke iron; then gradually warm to hot-blast coke iron, with the charcoal furnaces also heating their blast to get greater tonnages, and finally the present-day hot-blast coke irons with scrap additions to the ordinary burden that, according to one European report, have gone as high as 65 per cent. Parallel with this quality retrogression is the enormous increase in furnace tonnages from about 15 to over 1000 tons per day in exceptional instances of modern practice. The key to this situation is economic pressure. The effect is a growing differentiation between furnace production for gray iron and malleable foundries and, for the

Jan 1, 1927

By Ralph W. Smith

DEVELOPMENT of the lime industry- in Ste. Genevieve County began in a crude way in 1840. According to information furnished by the Missouri Bureau of Geology, in the early days small vertical kilns built of stone were used, and wood was the fuel. Modern development began in 1904 when one company introduced steel shells lined with firebrick. Within a few years two more companies erected similar plants, and in 1925 a fourth company began operations. Thus there are today four lime companies at Ste. Genevieve, all operating at high capacity and with a gradually increasing production. GEOLOGY The limestone of Ste. Genevieve County, which has the chemical composition and purity required for lime burning, is the upper 80 or 90 ft. of Spergen formation. The Missouri Bureau of Geology, in its geological map of Ste. Genevieve County, gives the Spergen formation a total thickness of 160 ft., but only the upper portion is pure enough for lime burning, with an average raw-stone analysis of 98.7 per cent CaC03; 0.35 Si02; 0.3 R203; 0.35 MgCO3; 0.3 S03. The Spergen, one member of the Meramac group, Iowa series, of the Mississippian system, underlies an area approximately 12 miles long north and south, by 5 miles wide east and west (Fig. 1) in Ste. Genevieve County. The entire eastern two-thirds of Ste. Genevieve County is sedimentary, the formations dipping gently toward the east on an average grade of about 4 per cent, or 2 ½ º. Thus the outcrops of the various sedimentaries run approximately north and south. A line running west from Ste. Genevieve crosses the outcrops of the sedimentaries, ranging from the top of the Mississippian to the Ozarkian geological system in a space of 12 miles. Thus with the gentle dip of 2 ½ º the 160-ft. thickness of the Spergen formation stretches out in its outcrop so that it is approximately one mile

Jan 1, 1938

By C. H. P. Lupis, Henri Gaye

There are m -I conditions for the stability of a solution of m components with respect to infinitesinzal flucturations. However, in most cases, only one of these conditions has to be considered to determine the domain of instability and the existence of this more restrictive condition greatly simplifies the calculations. It may be used advantageously for the prediction of miscibility gaps and the method is illustrated in details for the case of the Ag-Pb-Zn system. THE thermodynamic conditions for the formation of a miscibility gap may be viewed as a necessary consequence of the conditions for spinodal decomposition. A previous article1 has examined in detail the form of these conditions for multicomponent systems. There is only one condition for the stability of a binary system (with respect to infinitesimal fluctuations), but there are two conditions for a ternary system, and m — 1 conditions for an m-component system. The probability of violating a stability condition, and thus forming a miscibility gap, obviously increases with the number of components, a result which is rather intuitive since the atoms of the solution have now many more ways of redistributing themselves and introducing complexities in the form of the free energy hy-persurface. It is of interest to take advantage of this possibility of precipitating new phases and to examine which stability condition is the likeliest to be violated, that is, which stability condition is thermodynamically the most restrictive. The finding of such a condition would greatly simplify the application of the stability criteria since only one condition could then be considered, instead of m - 1. In Ref. 1, coherency strain energy terms were neglected, thus restricting the applications of the treatment to solutions where they are negligible, such as liquid alloys. In the following study the same assumption will be made. To generalize the treatment to systems where the strain energy terms are sizable, the reader is referred to Cahn's classical article on spinodal decomposition.2 Let us designate by Gij the second derivative of the Gibbs free energy with respect to the number of moles ni and n j. There are several equivalent sets of m — 1 stability conditions.' The one considered here expresses that the successive diagonal determinants of order 1, 2, ... m — 1, associated with the symmetric Gij matrix (for 2 5 i, j 5 m) are positive.' For a binary solution 1-2, the condition for stability is: O(u=G22^0 [1] For a ternary system 1-2-3, the condition [I.] is re- tained (the value of G22 will differ, of course, according to the concentration of 3) and another condition is introduced: £>(21 = G22G33 - Gl3 ^ 0 [2] In a composition diagram, these two conditions define two domains of instability. Starting at a point where the solution is stable (for instance at a point where the solution is very dilute) we gradually change the composition until the condition [I] or [2] is violated. As already noted in the literature, e.g., in the work of Prigogine and Defay,3 it is the boundary of the domain (2) which is first crossed. For if we assume that the boundary of the domain (1) is reached first, at this point G22 = 0 and the second condition is necessarily violated (D(2) = -& 5 0), in contradiction with our original assumption. An exhaustive study of the ternary regular solution case may be found in the work of Meijering.4 Moreover if the boundaries of the two domains have a common point, they also have a common tangent. For if the two lines were to cross each other as is illustrated in Fig. 1(a) any point M in the line QP would be such that £> = 0 and 0"' > 0 which, as shown above, are incompatible results. Thus, the two lines must be tangent at their common point Q as illustrated in the example of Fig. l(b). The reasoning of Fig. l(a) implies that the point Q is not a "singular" point for either boundary line. This singularity may be of two types. First, the lines meet without crossing each other and without being tangent. Second, the tangent at Q for D"' or 0"' is not single-valued. Other types of singularity are unlikely because of the usual analytical forms of D"' and 0"'. The exception to the common tangent requirement due to the first type of singularity was pointed out by John Morral;5 it occurs when the common point, Q' or (3" in Fig. l(b), is located at a boundary of the composition diagram, e.g., at the line X3 = 0. It may also be noted that at the common nonsingular point Q of D(1) and D(2), Fig. 1(b), G23 is necessarily equal to zero, whereas at a point such as Q' or Q", this conclusion is no longer valid because the product G22G33 is now indefinite (of the form 0. a). The exception to the common tangent requirement due to the second type of singularity occurs when two branches of the same boundary line intersect, for example when D(1)or D(2) decomposes into a product of functions, at a point which belongs to the boundary of the other condition. It is possible to show by a simple analytical calculation that, in this case, if Q is a singular point of D(1), then it is necessarily a singular point of D(2), and that the reciprocal is true except if G33 = 0 at Q. For the present article, however, more elaboration on these singularities appears to be unwarranted. To generalize the previous results to an m -component system, we use the mathematical theorem stating that if the diagonal determinant D(r) = 0, then

Jan 1, 1970

By George Holderer

THE Enos Coal Mining Co. owns an area underlaid by coal, of approximately 5000 acres. This property is situated 9 miles from Oakland City, in the southern part of Indiana. The mine has been in operation 5 years, during which time some 350 acres have been stripped, and stripping is now proceeding at the rate of about 100 acres per year. TOPOGRAPHY These coal lands consist of gently-rolling agricultural fields which in times past were farmed for wheat. There is no timber and but very little brush to contend with. The overburden varies from 10 to 60 ft. in depth. A thin bed of slate overlies the coal, followed by limestone, which varies from 3 to 15 ft.; this, in turn, is followed by sandstone, slate, shale and clay. There is a very wide variation in the thickness of all of these beds. The coal has an average thickness of 5 ft., and is a good grade of high-volatile bituminous. MINING OPERATIONS Briefly, the sequence of operations is: drilling holes with churn drills; blasting with L. 0. X.; stripping overburden to, uncover coal and, finally taking up the coal, which is sent to a tipple for cleaning and sizing. In order to show what is being accomplished by the use of L. 0. X., results will be shown from May to November, 1926, inclusive, and compared to the same period in 1925. No work was done in No. 1 pit during May, 1925, hence all figures are unduly low for this month.

Jan 2, 1927

By Carl Swartz

METALLURGISTS differ considerably in their opinions regarding the effect, if any, of small amounts of iron pyrites, or other iron compounds on zinc sulfide ores during the roasting operation. As a result, the literature on this subject expresses many conflicting ideas. The ore, previously crushed to pass through a one-millimeter screen, dries in the roasting kiln, losing water up to 200° to 300° C. At 150° C. iron pyrites begin to lose sulfur. As the temperature increases, while the ore is passing to the hotter part of the furnace, the sulfur burns to sulfur dioxide, leaving the metals as zinc oxide and ferric oxide. These two substances then interact to form zinc ferrite, a compound, yellow brown in, color, having the general characteristics of a spinet Like magnetite, another spinel, zinc ferrite is insoluble in alkalis and dilute acids. As a result, when leached with 10 per cent. sulfuric acid solution zinc values tied up in this compound remain behind. HISTORY In the electrolytic recovery of zinc from its ores, the roasted ores are usually leached with a 10 per cent. sulfuric acid solution. When the zinc ore contains iron pyrites as an impurity in an appreciable amount, the actual yield of metallic zinc is much lower than a theoretical calculation would indicate. Further, losses of zinc are, in a rough way, directly proportional to the amount of iron pyrites or other iron compounds present. When the iron is present in the ore in an isomorphous relation to the zinc, as in the case of a marmatite, a greater amount of zinc remains insoluble than when present as a true pyrite or marcasite. Work on the insoluble residues obtained from leaching of the calcines shows that the zinc lost is intimately tied up in this residue. Some investigators have suggested a definite compound, such as zinc ferrite, others merely a mixture of zinc and iron compounds.

Jan 1, 1927

By W. M. Albrecht, W. D. Klopp, R. I. Jaffee, B. G. Koehl

Kinetic studies were made of the reactions of tantalum with oxygen, nitrogen, and air at 400o to 1500°C. The tantalum-oxygen reaction is linear from 500° to 1250°C. The tantalum-nitrogen reaction follows a cubic rate law at 400° to 700°C and a parabolic rate law at 800" to 1475°C. The reaction behavior in air is initially parabolic followed by a transition to linear behavior. In the search for high-temperature materials, considerable interest is being shown in the refractory metal, tantalum. It is the third highest melting metal with a melting point of 2996°C. Also, tantalum has excellent ductility, making it one of the most workable refractory metals. In considering high-temperature applications of tantalum, the oxidation kinetics of the metal must be known. Such information also serves as a basis for the development of corrosion resistant tantalum-base alloys. Therefore, this study was made to investigate the reaction of tantalum with air, nitrogen, and oxygen. LITERATURE Several oxides of tantalum have been reported. The pentoxide, Taz05, is the only oxide of tantalum whose identity has been established. A high-temperature modification, aTa2Os, has been reported by several investigators.1-4 A low-temperature phase, ßTa2O5, undergoes an allotropic transformation at 1320o to 1350oC. 5-8 Four other oxides of tantalum have been reported. The oxides TaO2, TaO, and Ta4O have been reported by schonberg.9 A suboxide Ta2O, was observed by Wasilewski 6. However, the presence of oxides lower than Ta2O5 is questioned by Lagergren and Magneli.7 In oxidation studies, vermilyeal0 and Peterson, et al.,12 reported one possible phase intermediate between Ta and Ta2O5. Only Ta2O5 was formed in the tantalum air reaction, as reported by Michae1.l3 Several studies have been made on the kinetics of the tantalum-oxygen reaction. vermilyeal4 investigated the range 50° to 300°C and found that the rate of growth of a thin adherent oxide film could be described by the Cabrera-Mott theory. Gulbransen and Andrew15,18 studied the reaction kinetics of tantalum in oxygen pressure of 1/10 atm at 250° to 450°C. At all temperatures the reaction followed the parabolic rate law for periods up to two hours. The oxidation behavior in the range 500" to 1000°C was found to be linear at oxygen pressures of 0.2 to 600 psi according to Peterson. et al.l1 At very low pressures (1 x 10-3 to 2 X lo-' mm of Hg) Gebhardt and seghezzi17 reported linear oxidation at 800° to 1500°C. The reaction of tantalum with air is similar to the reaction with oxygen. Studies have been made by Waber, et a1.,12 and Michae1.l3 Two nitrides of tantalum, TaN and Ta2N are known. Their structures have been determined by Brauer and Zapp 18,19 The tantalum-nitrogen reaction kinetics have been investigated by Gulbransen and Andrews. 15, 16 The reaction follows the parabolic rate law at 500° to 850°C at a nitrogen pressure of 1/10 ,atm. At the same temperature, the tantalum-nitrogen reaction is much slower than the tantalum-oxygen reaction. EXPERIMENTAL TECHNIQUES Material— The material used in this study was high-purity, electron-beam-melted tantalum obtained from the Temescal Metallurgical Corp. The hardness of the as received ingot was 76 Vhn. The analysis of the material is given in Table I. Methods—Cylindrical specimens of tantalum approximately 0.9 cm in diam and 0.5 cm in length

Jan 1, 1962

Jan 1, 1881

By Theodore J. Hoover

WHAT are the chief branches of the mining engineering profession today? In an effort to analyze the structure of the profession, for practical purposes, a quantitative study has been made of the membership of the A.I.M.E., and is herein reported for the first time. In spite of the effect that a long history and a relatively small group of professional workers have had in limiting specialization in mining engineering, there has nevertheless grown up a wide variety of specialties in this field. More than a hundred different kinds of engineers were discovered among the titles given by Institute members in the Directory, ranging from "advisory engineer" and "American engineer" down to "wire-rope engineer" and "works engineer." How should all these titles be defined and interpreted? How many of them should be relegated as meaningless or confusing? What are the relationships among the remaining useful designations? Should some of them be grouped as "metallurgical" or "chemical," or under some other head?

Jan 1, 1935

Jan 1, 1902

By Mi Chung

T HE ore-dressing problem at Tul Mi Chung is complicated by the unusually complex nature of the ores. These come from replacement ore- bodies in limestone at the contact with a granite batholith, and contain copper, gold, silver, bismuth, molybdenum, iron, arsenic, zinc, and lead, the first two metals constituting the principal sources of profit. Iron is present as pyrite, magnetite, and hematite. Arsenic occurs both as mispickel and lollingite (FelAsa), the latter carrying a certain amount of finely divided gold. The gangue minerals are those typical of limestone con- tact-metamorphism and include a large percentage of garnet, together with diopside, serpentine, calcite, epidote, zoisite, actinolite, 'mica and other minerals. A part of the gold occurs in a free state; some is combined with chalcopyrite and lollingite, and a consider- able proportion is contained in the pyrite. Researches towards the improvement of recovery have been energetically conducted since 1915. Amalgamation, gravity concentrating tables, vanners, can- vas plants, etc., have all been tried and discarded in favor of flotation. It was very quickly established that fine grinding was essential for satisfactory recovery. This was and is still accomplished in Hardinge ball and pebble mills. A comparative test showed that when the ore was crushed to the point at which it contained 20 to 26 per cent. coarser than 100 mesh, the gold recovery was only 55.9 per cent., whereas when crushed so that only 11 to 15 per cent. was coarser than 100 mesh, the gold recovery was increased to 82.5 per cent. No particular difficulty was ever experienced in making a satisfactory recovery of copper but the losses in gold were considered serious and led to the investigation described in this paper.

Jan 1, 1924

By P. Payson

INTERGRANULAR corrosion in corrosion-resistant chromium-nickel steels has been widely discussed in the last few years. So far as the author knows, nothing has been published which definitely shows that this tendency can be eliminated, although suggestions have been made that a remedy is possible if certain specifications are satisfied. Strauss, Schottky and Hinueber1 suggested an increase in chromium content to an extent that would prevent the impoverishment of chromium on carbide precipitation sufficient to cause impaired corrosion resistance in the matrix. Pilling2 suggested an increase in nickel, so that the stability of the austenite matrix would be increased. Aborn and Bain,3 say that "intergranular attack-may be eliminated by preventing carbide precipitation (e. g., by lowering the carbon content or somehow raising its solubility) or by precipitating it permanently under conditions which will not remove chromium from solid solution so drastically at any points." In a later paper Aborn and Bain4 state that many different metallic elements, tungsten, vanadium, copper, aluminum, molybdenum, titanium and zirconium, have been added in small per-centages to increase the stability of these alloys, but that it has been reported that according to the copper sulfate test these added elements act only to retard the intergranular corrosion, and that increased nickel and chromium contents have similar effects. Newell5 showed that the lower the quenching temperature before reheating, the less severe was the intergranular attack.

Jan 1, 1932

[ ]

Jan 1, 1946

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By G. L. Schroeder

Investigations were conducted at two underground locations, foreman's room and 5702 area, of the Kermac Nuclear Fuels Corp. uranium mining installation, Ambrosia Lake, New Mexico. The rock environment is stratified sandstone. Pressures were varied from minus 0.4 an Hg to plus 3.8 cm Hg with respect to barometric pressure, and were maintained for periods ranging from several hours to 21 days. One cm Hg overpressure (-1.5% of normal barometric pressure) produced a 20-fold decrease in Rn flux into the foreman's room as compared to the Rn flux observed during dilution ventilation. The 5702 area experienced a 5-fold decrease in Rn flux for a similar overpressure. During 21 days of continuous 1 cm Hg overpressure in the 5702 area this reduced Rn flux was maintained. The smaller reduction in flux for the 5702 area results in part from the proximity of the foreman's room to a non-pressured area and the presence of an impermeable shale lens overlying the ceiling of the 5702 area. A 0.4 cm Hg underpressure of the 5702 area increased the Rn flux into the area by 3-fold over the non-pressured value. A barometric pressure influence on Rn flux into the mine and on air Rn concentrations in non-pressurd areas of the mine was measured. A falling barometric pressure causes an increase in the flux of interstitial gas into the mine; a rising barometric pressure decreases this flux. These effects are not seen in overpressured mine areas. Radon concentrations in rock interstices show, during overpressure, decreases of all locations monitored except in the immediate vicinity of the shale lens above the 5702 area ceiling. These reductions are the result of air flowing from the mine into the rock interstices under the influence of the pressure gradient induced by the overpressure. The relative humidity of the 5702 area was reduced after 2 days of 1 cm Hg overpressure from a pre-overpressure value of 96% to 81%. The control of harmful or noisesome gases which emanate into underground mining areas from surrounding rocks is often a costly necessity. In uranium (U) mines this problem is presented by the high interstitial concentrations of radon-222 (Rn), a radioactive noble gas of 3.82-day half-period, formed in the decay scheme of U238, and the relative ease with which this noble gas diffuses from its parent rock into the interstices of the rock and then to a working area. Long-term exposure to moderate concentrations of Rn (3000 µµc per 1) and its short-lived alpha-ray emitting daughter products, RaA (Po218) and RaC (po214), has been found to result in an increased incidence of bronchial carcinomaa2 The acceptable limit of Rn daughter products in a mine atmosphere is presently set at a concentration of short-lived radon daughters which would be in equilibrium with 100 ppc of Rn per 1 of air. Ventilation of mines is conventionally accomplished by continuously diluting the mine air with fresh air brought in by fan or natural convection from above ground surface. The diluted air is allowed to vent freely to the atmosphere. This process does nothing to retard the rate at which gases (including Rn) diffuse into the mine from surrounding rock. It merely reduces the concentrations of these gases within the mine. It is suggested that in a sufficiently permeable rock environment a slight pressurization of the mine air may induce air flow from the mine into the interstices of rock surrounding the mine. The convective flow of comparatively fresh air will reduce the concentration and the concentration gradient of undesirable gases in the rock interstices adjacent to the mine. Radon will diffuse counter-current to this convective flow at a rate proportional to its concentration gradient. In time, a steady state of convection and counter diffusion will be established. The Rn flux into the mine will never be reduced to zero, and will only asymptotically approach zero as the overpressure (and hence the convective velocity of purging air) approaches infinity. During 1963 and 1964, an investigation into the effect which such applied pressures have upon the Rn characteristics of a mine atmosphere was conducted at the Kermac Nuclear Fuels Corp. uranium mines, Ambrosia Lake (near Grants), New Mexico.

Jan 1, 1967

By N. H. Emmons

An interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at its plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory. Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaccs. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top mas necessary and the engineering force was started on the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of east copper, but the heat was great that the copper bent readily, due to the jarring of its

Jan 1, 1911

By D. B. Hobbs, L. W. Kempf, R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13 per cent. of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 25S, Special 17S and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings. REVIEW OF LITERATURE The literature on the heat treatment of aluminum-silicon alloys is not very extensive. The following review gives the principal references of which the authors are aware, in which appreciable information may be found.

Jan 1, 1928