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By Hugh Roberts

During 1916 and 1917, the E. J. Longyear Co. of Minneapolis, Minn., carried out a campaign of exploration for nickel-copper ore in the Sudbury District of Ontario. The work was initiated by W. E. Smith, a resident of Sudbury, who called the attention of W. J. Mead, Chief geologist. The E. J. Longyear Co., to the fact that explorable lands in the Sudbury District were still available. Five diamond drills were employed, and holes were drilled in the townships of Levack, Trill, Denison, Blezard; Garson, Falconbridge and MacLennan. The general map of the District, Fig. 1, shows the distribution of the lands chosen. As a result of this exploration, a large body of nickel and copper ore has been found in the western part of the Township of Falconbridge. This property lies in the eastern part of the Sudbury District, east of the Garson mine.

Jan 2, 1918

By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

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

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By Frederick Bacorn

THE paper of Reno H.. Sales on Ore Deposits at Butte, Mont.,' is a careful and painstaking work, an important contribution to the literature of the subject. As is almost inevitable in a work of such magnitude, a few misstatements occur; and some of these I shall endeavor to point out. Mr. Sales has also fallen into error, as I think, in the application of his theory of ore deposition; and while the modification which I venture to suggest is a minor one geologically, it is of great economic importance. I refer to Mr. Sales's idea of an outward migration of mineralizing solutions from a supposed central copper zone. In order that I may make myself plain, I must first epitomize the theory as a whole, which I understand to be this: All of the Butte ore deposits (save those along the Continental fault, not herein considered) are derived from solutions of magmatic origin, which, at the beginning of their ascent from a great depth, were, acid in reaction, hot, and were carriers of copper, zinc, manganese and other metals. As they departed from their point of origin they lost heat, and, because of reactions with the wall rock, became more and more alkaline. The metal deposited from these solutions in their hot condition was principally copper; and, as they cooled, they deposited less and less copper and more and more manganese and zinc, until the copper practically disappeared. With this theory in general I have no fault to find, nor have I, it must be stated, the qualifications necessary to enable me to pass upon it critically; but it seems to me to be reasonable and probable, and is one which I am quite willing to accept.

Jan 8, 1914

By D. J. McAdam, R. W. Mebs

The technical cohesive strength of a metal means, not the interatomic forces, but the technically estimated resistance to fracture. An example of such resistance to fracture is the so-called "true" breaking stress of a tension-test specimen, the breaking load divided by the sectional area at fracture. According to the prevalent view,8 the technical cohesive strength of a metal. in any particular state as regards prior mecharlical treatment and heat-treatment, is determined by a limiting value of the algebraically greatest principal stress. In two previous papers by one of the authors, evidence was presented to indicate that the technical cohesive strength of a metal cannot be represented by a single stress value, but that it comprises an infinite number of values corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength thus comprises an infinite number of technical cohesion Limits, each representing a specific stress combination at fracture. In the same papers, evidence was presented that plastic extension causes a continuous increase in the technical cohesive strength. Such a variation is not in accordance with the prevalent view that plastic extension first increases, then decreases, the technical cohesive strength.' In this paper, as in the previous papers,14.15 the algebraically greatest principal stress will be designated S1, the least principal stress will be designated 33, and the intermediate principal stress will be designated S². The technical cohesion limit under polarsymmetric tension (S1 = S2 = S3) will be termed the "disruptive stress," and the cohesion limit under unidirectional tension (S2 and S3 = o) will be termed the "severing stress."l4, .l5 The yield strength of a metal, according to the generally accepted theory, may be represented by a constant value of the shearing-strain energy, and hence by a constant value of the sum of the squares of the three principal stress differences. In the second of the previous papers,15 however, evidence was presented that the limiting yield stress decreases with increase in the volume stress, the algebraic average Of the three principal stresses.* This in fluence of the volume stress becomes prominent only in the field of triaxial tension. In the two previous papers,".'5 diagrams were presented to show the variation of the technical cohesion limit, yield stress, and ultimate stress with the combination of principal stresses and with plastic extension. Those diagrams and the resultant • Any stress system ma? be resolved into a polarsymmetric stress causing pure volume strain and a combination of pure shearing stresses. which cause no change of volum

Jan 1, 1945

Sailing westward from the Society Islands in the fall of 1774, England's noted explorer Captain James Cook discovered New Caledonia-that long, linear island that has played such an important and varied role in the history of nickel. Upon his return to England the following year, Cook's announcement of this uncharted island generated governmental interest, but its distance from the Island Empire, the troubles in the colonies, and the difficulties with France combined to keep English interest indirect and in the background of the then-current events.

Jan 10, 1968

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

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Jan 1, 1946

By T. L. Joseph

The extent to which hot metal from the blast furnace affects open-hearth practice and the quality of steel produced has been discussed widely. Open-hearth operators have attributed difficulties experienced in making satisfactory steel to characteristics of the pig iron not disclosed by ordinary analysis. The commonest criticism of the iron has been that it is "physically cold" or "dirty." Often when the blast furnaces are working irregularly the quality of the iron is questioned. A cold hearth, slipping and hanging, the use in the past of unsintered flue dust, and the use of ores difficult to smelt have been associated with the production of iron of poor quality. The difficulty of the situation is that we have no proven yardstick for quality aside from ordinary analysis. Uniformity in analysis is recognized as being important, but the difficulty of changing the open-hearth practice when the iron analysis varies widely may not always be fully appreciated. Although the problem of correlating the characteristics of steel with those of pig iron is admittedly obscure, the effort of producers of quality steel to investigate all factors that may have a bearing on the final product is justified. This report contains data on the oxides in several hundred casts of basic iron produced in a furnace during the course of normal operation on Lake ores. Incidental to the study of the oxides in the iron, it was desirable to follow closely the temperature of the iron. The effect of temperature of the iron upon the silicon and sulphur present is discussed. A general relation between the basicity of the slag and the sulphur in the metal was developed. The amount and composition of oxides in the hot metal and in the steel bath during various intervals between melt-down and tap are discussed. Heats of rimmed steel, killed steel, and semikilled steel were investigated. The hot metal on individual heats was either all taken from a mixer or consisted partly of direct metal and partly of metal from the mixer. Samples of the iron for oxide determinations were

Jan 1, 1937

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 Jack A. Simon, M. E. Hopkins

GENERAL GEOLOGY Coal is defined as a combustible rock that had its origin in the accumulation and physical and chemical alteration of vegetation. Coal can be ignited and burned like the wood that was man's earliest fuel, but coal gives more heat than the same amount of wood and has many industrial uses. Unlike wood, coal is not generally found on the surface of the ground but is mined from the solid rock of the earth. Before taking up the occurrence, formation, and the somewhat unique character of coal in the rock sequence, let us briefly consider the general character of all rocks in the crust of the earth. Relatively little is known about the very earliest history of the earth, although a number of logical theories have been developed. Manned exploration of the moon and the rocks being returned to earth will, we hope, provide some answers to questions concerning the earth's origin and history. The period of earth history with which we concern ourselves here begins after great areas of water had evolved on earth and substantial land areas of once molten (igneous) rock existed. Weathering and other processes that attacked the surface of the rocks reduced them to small particles. Water provided by rainfall transported this material, ultimately, to large bodies of water where it was deposited. Thus was initiated the geologic sequence of sedimentary rocks that lie above the once molten igneous rocks. The crust of the earth is not completely stable, and throughout the geologic past portions of the crust have moved laterally and vertically. Even today, many coastal areas are slowly rising or sinking. More sudden earth movements are recognized by the earthquakes they cause. Throughout geologic history, rises in sea level or the sinking of the land areas have many times permitted the oceans to cover much of what are now the areas of the continents. Only relatively small parts of the present continents appear to have been above sea level throughout geologic time. Great

Jan 1, 1973

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 H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.' The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

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