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By W. H. Schacht

IN THE Lake Superior District, the air indoors must be heated continuously during eight months of the year and occasionally during the remaining months. Incident with mining in this district, therefore, there is need for heating many of the buildings connected with these operations. In addition to the mine buildings, that is, shops, engine, houses, offices, change houses, etc., such public buildings as schools, library, and theater, when close to the mines, are often supplied from the mine heating mains. At the Copper Range Company's mines, Champion, Trimountain and Baltic, the heating surface thus supplied from the mine mains is over 50,000 sq. ft. (4645 sq. m.) which requires a steam consumption, at times, of 18,000 lb. (8165 kg.) per hour, or the equivalent of a rate of over 50 tons of coal per day (were live steam used). This figure is based on a consumption of 1/3 lb. per square foot of heating surface during the coldest weather, and provided the system is not wasting steam by blowing it to the atmosphere or into the return line on account of leaky traps, which so often is the case. Under the latter conditions, steam consumptions of three to four times the above rate are not uncommon. This shows that the cost of heating is of enough importance to be given serious consideration, especially at this time of rising prices of fuel. The power and heating value of exhaust steam are appreciated by most engineers, and its application for such purposes is general. At our stamp mills, the exhaust from the stamps is used to operate low-pressure turbines, thus reducing the former water rate per horsepower developed by more than 50 per cent.

Jan 8, 1920

By H. H. Alexander

PRIOR to 1915, numerous attempts were made to treat tin concentrates in the United States, but for various reasons they were unsuccessful. Tin ore is said to have been found in nearly every state, but none of the deposits have proved to be of commercial importance. The only domestic production is in Alaska, but only a few hundred tons annually have been produced; hence any considerable production of tin in the United States must be from foreign ores. The most promising occurrence of tin was found in the Black Hills, S. Dak.; in the early development stage, it was called the Cornwall of America. Associated with the tin is tungsten. The story is told that an exceedingly fine specimen of the Black Hills ore was sent to England to encourage stock promotion; the desired effect was produced until a skeptic chipped off a small piece, which the analysis showed to be wolframite. FIRST ATTEMPTS AT SMELTING One of the first promising attempts at tin smelting in the United States was made by R. T. White at Bayonne, N. J., in 1903. Mr. White, after spending some time in England studying the methods of tin smelting, organized a company called the International Tin Co., and erected a plant to treat tin concentrates from the Straits of Malacca. About the time the plant was completed, the English Government placed an export duty of 40, per cent. ad valorem on tin .concentrates exported to other than British smelters, which duty made it impossible to operate this plant so the enterprise was abandoned. As this export duty is still effective, the only source of tin-ore supply for 'the United States is the Bolivian concentrates.

Jan 3, 1924

By Frank H. Riddle, Wilfrid R. Foster

GENERAL treatment of the various minerals of importance in refractories appears in the chapter entitled "Refractories" elsewhere in this volume. The present chapter is restricted to a discussion of minerals of the sillimanite group and brings up to date the excellent information contributed by Prof. Paul F. Kerr to the first edition (1937). Since the appearance of that edition, the status of the group has changed some- what. Kyanite remains the preferred source material for mullite refractories but total consumption of kyanite has increased considerably.85 The exigencies of World War II forced an increased dependence on domestic sources and led to an intensification of the search for higher-grade deposits of kyanite and allied minerals. The first discovery of massive kyanite similar to that of India has been reported from Georgia.37 British East Africa has joined India as a substantial supplier of our imported kyanite, but that from India continues to hold preference.85 During World War II, prices of both domestic and foreign grades reached peaks unparalleled since the earliest years of the use of kyanite and as yet have shown no tendency to return to prewar levels. Topaz, by virtue of the deposit outlined in South Carolina, merits inclusion in the group.20,36,95 Large andalusite deposits, which threaten to rival our one large domestic occurrence, have been found in Russia.69,88 Sillimanite has not yet attained an important position among these useful minerals because of the lack of accessible deposits of high-quality material in adequate supply.37,50,58 Tests by the Bureau of Mines have indicated the possibilities of economically beneficiating low-grade sillimanite and kyanite.105.106,140 Government, university, and industrial

Jan 1, 1949

By Joseph Hyde Pratt, Douglas B. Sterrett

Monazite is one of the minerals which, for a long time, was considered somewhat rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas arid Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals,ceriunl, lanthanum, and didymium,(Ce,La,Di)PO,. There is nearly always present a varying but small percentage of thoria, Tho2, and silicic acid, SiO2,, which are very probably united in the form of a thorium silicate, ThSiO4. Some mona-zites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent.; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellop. in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a con-choidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that werc 6 in. in length. The more perfect crystals are,-however,

Jan 1, 1910

By Carl Allen

INTRODUCTION IN any discussion of mining one is repeatedly confronted with the difficulty of dealing with so many variable conditions. It is not an exact science and in the choice of a method each varying factor has a certain weight, which, in many cases, experience alone can determine. In mathematical terms, it is a function of many variables. A discussion of mining also loses much of its value unless, costs are considered, because the expectation of profit is the only excuse for carrying on mining at all. As conditions vary they cause fluctuations in cost and there are few operations to which a definite cost can be assigned. The character of the ore may make it difficult to drill, yet because of the ease with which it breaks the total cost of drilling and blasting may be low. In preparing this article the attempt has been, not to cover the whole field of mining, but to describe the different methods of stoping and mining which have distinct principles. In addition to this an effort has been made to show the advantage of dissecting the methods into their detailed operations and applying to these a mathematical study as an aid to the judgment in determining which is the best method to adopt, or in attempting to reduce the cost of a method already in use. Methods of mining include stoping, caving, and various methods of working large deposits which, in addition to the method of actually breaking the ore, require elaborate and definite plans of, development of the orebody. The ordinary methods of stoping are too familiar to all for any elaborate discussion, but it has seemed advisable to review the subject and give the principal advantages' and disadvantages of the different methods.

Jan 8, 1914

By J. M. W. Mackenzie

Recent successful applications of emulsion flotation suggested that a detailed study of some of the physicochemical aspects of the process was warranted. The objective of the current research was to provide general information on the electrokinetic properties of emulsion drops of the type commonly used in oxide mineral flotation. Combinations of the parafin oil Nujol and several long-chain reagents in water were studied with respect to the effect of pH on the surface and zeta potentials. It war concluded that for emulsion drops in the presence of a long-chain reagent but in the absence of any other electrolyte which is adsorbed at the oil-water interface, the surface potential will be some two to four times the value of the zeta potential. During the last decade there has been a revival of interest in the so-called agglomeration, or emulsion flotation (in this paper the term emulsion flotation will be used), process. In this flotation technique, a neutral hydrocarbon oil, together with longcnain reagents, usually of a polar-nonpolar structure, are added to the pulp to function as collectors for specific minerals. The combination of oil and longchain reagent is either emulsified prior to addition to the pulp, or in the pulp itself, and the resulting collector species is an oil-in-water emulsion of a neutral hydrocarbon oil emulsified by polar-nonpolar long-chain reagents. Emulsion flotation has been used successfully in the treatment of ores containing iron, manganese,' and titanium oxides. 2 Two other major and long established applications of emulsion flotation are the flotation of coal and Florida phosphate ores. In recent years, emulsion flotation has been particularly successful in the treatment of ores containing oxide minerals which slime readily and, consequently, are difficult to treat by conventional flotation processes. The recent successful

Jan 1, 1970

By Richard Smith

After a brief history of the phosphate industry of Tennessee, the distribution and origin of the phosphate rocks are described. Then the mining and treatment, together with costs of production, and the uses of the rocks are given. THERE are three distinct varieties of phosphate rock, in Tennessee, known commercially as: (a) the "brown" rock, which is the residual product of the weathering and natural concentration of certain phosphatic Ordovician limestones; (b) the "blue" rock, which is an unaltered phosphatic stratum of Mississippian or Devonian age; and (c) the "white" rock, which is the result of chemical replacement and deposition. Before 1894, South Carolina and Florida had supplied most of the phosphate of the United States, South Carolina leading until that date and Florida from then until the present time. In December, 1893, the blue phosphate of Tennessee was discovered almost simultaneously on Swan Creek, in Lewis County, by two independent parties-by one as the result of a careful and systematic search for a workable deposit of the long known kidney phosphate, and by the other through mistaking it for a "bloom" of coal. Leases were taken and, with further prospecting disclosing other deposits in the region, the development progressed as rapidly as could be expected without railroad transportation. In January, 1896, Judge S. Q. Weatherly, who was interested in the development of the blue phosphate, while riding along the road south of Mt. Pleasant, noticed some slabs of a brown rock in place above the limestone. He took samples, and had them analyzed, thus discovering the high-grade brown phosphate of this district. This discovery was kept a secret until July, 1896, when mining was started at the village of Mt.

Jan 9, 1924

By H. A. Baumann, A. J. Rostosky

EVER since the first installation of wet-washing methods of coal preparation, the removal of the water added by the washing process has created serious technical and operating problems. The rapid development and widespread adoption of wet washing has necessitated a corresponding development of dewatering methods and equipment. The amount of water retained by coal varies with the size of the coal. The moisture that is largely on the surface of the particles is easily shaken off coarse coal; thus coarse coal can be dried comparatively easily and quickly. Fine coal presents a larger surface area than does coarse coal, so its capacity for retaining moisture is greater. In fine coal, moisture below about 5 per cent is held between the coal particles and its removal is difficult. Draining and drying of the finer sizes is a major problem at many washeries. Two common problems of coal-washing practice that are intimately connected with dewatering and drying are the clarification of washery water and the prevention of stream pollution. The first field has been studied from many angles, including the use of coagulating and settling agents followed by vacuum filters to remove the solids, and the use of sludge tanks with dewatering screens incorporated therein. In many districts, the disposal of sludges into streams has been stopped by law. The lack of space for impounding sludges has created problems of disposal in other districts. Reduction in moisture means a saving in freight costs as well as the elimination of difficulties in unloading and storing. Excess moisture in coal causes it to freeze in localities where severe climatic conditions pre¬vail. Excess water in coals to be used in the production of coke and manufactured gas has a chilling effect on the walls of the oven or retort. Dryness of coal is important in producing good briquettes.

Jan 1, 1943

By R. W. Winson

Asbestos is the generic name given to a group of fibrous mineral silicates found in nature. They are all incombustible and can be separated by mechanical means into fibers of various lengths and cross sections, but each differs in chemical composition from the others. The commercial grades of asbestos consist of a spectrum of lengths and sizes and are not definitive as are most organic fibers. It is generally recognized that there are two main groups of asbestos. The first only contains the fibrous serpentine called chrysotile and comprises about 94% of the world production of asbestos. The second group contains five minerals in the amphibole series+rocidolite, amosite, anthophyllite, tremolite, and actinolite. The latter two have no commercial importance. Properties Physical The structures of asbestos fibers have been studied intensively over a number of years. X-ray diffraction patterns have been used as a means of identification and classification. Low angle X-ray scattering techniques have shown that chrysotile fibers are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 18014 to 300A units, while the amphibole fibers are many times larger in cross section. Electron micrographs of the more common types of as- bestos are shown in [Figs. 1-4]. [Fig. 1] illustrates the softness and flexibility of chrysotile which make it suitable for textile-type products. For a number of years there was considerable controversy over the exact nature of chrysotile fiber, but the photographic evidence in [Figs. 5-7] clearly show that it is tubular in structure. The curvature is the result of the mismatch in the dimensions of the silica [Si,O,l and brucite [Mg(OH),] layers which are on the inside and outside, respectively, of a double sheet. This curvature had been predicted by Pauling (1930) years ago based on the molecular dimensions of the two component structures.

Jan 1, 1975

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metallurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each temperature from room temperature to fusion temperature, and cooled at a rate that is not generally controllable but is predetermined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each temperature zone. The nature of the zones produced by other types of welding is the sane. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and disadvantages of the extent of the zone are of prime moment, and are discussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known. GENERAL METHOD The scheme of procedure in the work herein reported involved the testing of the metal of each temperature zone adjacent to the weld in so

Jan 1, 1935

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less.

Jan 1, 1938

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By P. Douglas, G. M. Leak, B. Mills

The sinusoidal surface relaxation technique has been used to measure the surface self-diffusion coefficient of spectroscopically pure nickel over a wide temperature range under a hydrogen atmosphere. A kink in the Arrhenius plot has been observed. In the temperature range T/T 0.98 to 0.80 (T in O K and T, is the melting temperature) the average self diffusion coefficient is given by Below the temperature T/T,- 0.80a decrease in the slope of the log Ds us 1/T plot is observed. This is associated with a diffusion process characterized by a lower activation energy (-20,000 cal mole'') and smaller preexponential term (-10- sq cm sec"). A series of experiments were carried out at T/Tm = 0.61 under a hydrogen atmosphere of higher oxygen partial pressure than for the rest of the experiments. It was found that Ds was significantly depressed due to oxygen adsorption. This evidence supports the opinion that the low temperature process (activation energy -20,000 cal mole-') is unlikely to be due to oxygen adsorption. An interesting feature of the present data is that the transition temperature (T/Tm - 0.80) is a function of orientation. For a small number of crystals of measured orientation the transition temperature was observed to be higher towards the low index (100) pole. Theories of surface diffusion are briefly reviewed and it is concluded that the present reszuts are best explained by invoking a surface roughening process. GJOSTEIN has recently analyzed available surface diffusion data for a wide range of metals. He suggested that two mechanisms were operative for fcc metals, an adatom process at high temperatures and a vacancy process at low temperatures. Results for nickel can be summarized as follows. At low temperatures (T/T, - 0.3 to 0.44) under ultra high vacuum conditions, Melmed2 measured an activation energy Q of 21 kcal mole-' using field electron emission microscopy. At higher temperatures (T/T - 0.7 to 0.9) under a vacuum of 10- ' torr, Maiya and lakel measured y as 39 kcal mole-' using the multiple scratch smoothing technique. The present work was undertaken to try to find out if two distinct processes could be observed. High temperature results give Q about 47 kcal mole-': there is evidence also for a low temperature value of about 20 kcal mole-'. These measurements were all made under a hydrogen atmosphere, in the temperature range 860" to 1412°C. Concurrent with the present study Bonze1 and jostein> have also observed a break in the Arrhenius plot for the (110) surface of nickel. These measure- ments under ultrahigh vacuum conditions using the laser diffraction technique are in excellent agreement with the work reported here under hydrogen annealing conditions. THEORY The available surface relaxation techniques include single and multiple scratch smoothing and grain boundary grooving. The processes have been compared in detail by Gjostein for conditions where surface diffusion dominates6 and Mills et al? where volume diffusion dominates. In summary the relevant points are as follows. Grain boundary grooving gives an average Ds for the two surfaces adjacent to the boundary and this can, to some extent, be simplified by using symmetrical bicrystals. This technique has been used to study the effect of environment on Ds for silver and copper.'-'' Scratch techniques yield Ds values for the small orientation range exposed by the scratches (-2 deg). The multiple scratch process is preferable because the profile rapidly becomes sinusoidal and can then be interpreted theoretically in a relatively simple way. Also corrections for mass transport processes other than surface diffusion can be introduced easily. Mullins" considered a sinusoidal profile described the wavelength of the profile. After time t the profile can be described by the equation The terms A, A', C, and B which account, respectively, for contributions due to evaporation-condensation, diffusion through the gas phase, volume diffusion through the lattice, and surface diffusion are defined as: where Ds = the surface self diffusion coefficient ys = the surface energy per unit area p = the equilibrium vapor pressure over a flat surface pa = the equilibrium vapor density over a flat surface DG= the diffusion coefficient of vapor molecules in the inert gas DM = the mass transfer diffusion coefficient which for a pure cubic metal is Dv/f where Dv is the radiotracer diffusion coefficient and f is the correlation factor H = the molecular volume V = the surface density of atoms, il2'3 M = mass of an evaporating molecule

Jan 1, 1970

By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers' vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thick-ners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.' The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter. It is quite apparent from reading the literature that Coe and Clevenger's contribution is not generally appreciated. In so far as the basic engineering relationships are concerned, the only real advance which has occurred in the 30 odd years which have elapsed since the Coe and Clevenger paper is the recognition of the effect of the rakes on the thickening process. Bull and Darby2 noted this in 1926, and the extensive use of the "gluten type" thickener, in which the effect is magni-fied, bears witness to its importance. Comings3 further verified this effect of the rakes. As a matter of fact, a number of papers show an apparent regression from the Coe paper in that the area determinations are made on the basis of a single test from One concentration of solids. Coe and Clevenger amply demonstrated that this is unsafe, since the controlling zone may be one other than that of the feed dilution. Comings3 neatly demonstrated this without apparently realizing it. Of course there have been significant advances in the application of the operation to industry. Open tray thickeners were introduced to save area; balanced tray thickeners, washing thickeners, and multifeed clarifiers were developed with all of their special hydraulic and mechanical problems. Combinations of all kinds have been introduced, such as combination agitators and thickeners, combination flocculators and clarifiers, combination thickeners and filters. With the establishment of the operation on a firm engineering foundation, installation was facilitated and expansion proceeded. There are still problems, of course, functional as well as mechanical. Sometimes the moisture in the underflow obtained in practice is not as low as is expected on the basis of the test data. Sometimes the underflow is so "thick " that its discharge and subsequent handling requires special attention. Island formation plagues some operators. The use of the thickener as a surge basin and blending tank in the cement industry poses unusual problems. Design of rakes and the drive mechanism must be continually im-proved. Corrosion problems must he overcome. Power requirements for raking the settled solids occasionally is the controlling factor as it was in the case of the all American Canal desilting installation. Other similitude relationships and design problems come into the picture when we enter the field of clarification or nonline settlement. We have an energy dissipation problem in introducing the feed and any models must satisfy the Froude model relationships. Autoflocculation requires detention which involves the same similitude laws that we encounter in the compression zone. Approach to an Exact Science The next step beyond having control of the similitude relationships is to understand the why of these relationships right back up the line to first principles. The ultimate might be that, if given the mineralogical composition of the solids and their size distribution together with an analysis of the suspending liquid, we could calculate the entire thickening behavior of the system. Then we could say we had reduced the operation to an exact science. True it might be more trouble getting this basic analytical data than to make our empirical determinations for area and volume, and we would need an ENIAC to calculate the results, but that does not detract from the desirability of such understanding. Considerable work has been done by the chemical engineers with this end in view. Comings,3 Egolf,4 Work,5 Kam-mermeyer,6 Steinour,7 and others have studied the problem. The writer has no final answer to the thickening story but would like to propose a picture of the mechanics of the two phases of thickening which has been found useful in understanding the subject and which leads to some convenient relationship in treating the compression step and arriving at the compression depth.

Jan 1, 1950

By Everett H. Graff, Ray H. Misener

THE Sol de Oro mine is in the province of Nazca, 487 km. southeast of Lima, and 60 km. inland from the coast at an elevation of 1200 m. above sea level. From Lima the mine may be reached in 8 hr. by automobile; 472 km. from Lima to Nazca over the paved Pan-American Highway and 15 km. from Nazca to the mine over a good graveled road. The trip from Lima can also be made in 2 hr. via the Faucett Air Lines which make two stops weekly at Nazca. The [Compania] Aurifera Nazca, owning and operating the Sol de Oro mine, was organized in Lima in 1930 by a group of prominent Peruvian mining men, including Ing. Carlos Alvarez Calderon, Dr. Alfredo Alvarez Calderón, Ing. Hector Boza, Ing. Jorge Félix Remy, Ing. Eulogio Femandini, Sr. Fernando Wiese, and Sr. Julio East. The nine claims in the Sol de Oro group owned by the company comprise an area of 52 square kilometers. Development of the property was not started until 1932 and only then under adverse conditions, owing to lack of transportation facilities. Mining machinery and other supplies could be taken as far as Ica by boat and railroad, but to transport them over the 180 km. of hot, sandy desert from Ica to the mine was a problem. There was no road in those days and only a few of the most venturesome truck drivers cared to contract the hauling. Another problem the company had to face was that of securing adequate labor. The Sol de Oro is in an agricultural region, and was forced to look to the near-by cotton plantations for men. Experienced men were imported from the "sierras," but they did not stay. The men are accustomed to high altitudes and cold climate and cannot easily acclimate themselves to the hot and arid coastal region. As a consequence the company has been forced to hire the inexperienced local laborers and train them for mining. The company has established three separate camps at the Sol de Oro property. Each is approximately one kilometer from the other and connected by auto road. The upper mine camp consists of living quarters for 300 workmen and their families, a general mine office, carpenter shop and timber-framing shed, compressor house, drill-sharpening and drill-repair shop, first-aid station, time office, school and store. At the central or "empleados" camp there is a 200-ton cyanide plant, general offices, warehouse, powerhouse, shops, laboratory, hospital, school, guest house, an 18-room hotel for the single staffmen, and 12 completely modern five-room cottages for the married staff employees. At the lower camp are living quarters for 200 workmen and their families, two general stores, a school and a small theater. Below this camp, along the river, are the company wells and pumping plant supplying water for mine, mill, and camp uses.

Jan 1, 1945

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By O. D. Gonzalez, H. A. Wriedt

Alloys ranging from pure iron to pure nickel were saturated with nitrogen gas at 918°, 999°, and 1217°C and analyzed. The solubility of nitrogen at 1-atm pressure was obtained as a function of nickel content for the whole range of iron-nickel alloys and the temperature dependence of solubility is shown for the experimental alloy compositions. The heat of solution and the entropy of solution of nitrogen in the alloys as func-tiom of composition up to 41 pct Ni are given. 1 HE acquisition of more exact thermodynamic information for systems composed of iron with various alloying elements continues to interest ferrous metallurgists. The interstitial alloying elements, especially carbon, hydrogen, and nitrogen, comprise a field of particularly intense study. A recent investigation of carbon solubility in Fe-Ni alloys held at 1000°C in gases of fixed carbon activity showed an unpredicted minimum in the solubility near 72 pct Ni.1 The present investigation was undertaken to see if a similar anomaly in solubility existed for nitrogen in Fe-Ni alloys. The solubility of nitrogen in ? iron at known nitrogen activities has been measured several times.&apos;-&apos; Corresponding information for the solubility of nitrogen in solid Ni and Fe-Ni alloys is not available. Juza and sachsze9 reported that metallic nickel dissolved 0.07 pct N in equilibrium with Ni3N at 445°C. This result was regarded as dubious by Turkdogan and Ignatowicz10 who found less than 0.0004 pct N in nickel specimens equilibrated at 600°C with ammonia-hydrogen mixtures having fugacities of N2 gas up to 35,000 atm. Such fragmentary reports indicate only that nitrogen gas has a very much lower solubility in nickel than in iron. MATERIALS A purified iron from Battelle Memorial Institute was used for solubility measurements. This grade contained more than 99.95 pct Fe, the highest content of any measured individual impurity being 50 ppm for each of As, C, Cu, and Pb. The nickel and iron-nickel alloys, supplied by the International Nickel Co., contained 0.02 to 0.04 pct C, 0.17 to 0.19 pct Mn, 0.04 to 0.08 pct Si, < 0.01 pct P, <0.03 pct S, and <0.20 pct Co as principal impurities. The Fe-0.59 pct Mn alloy was of zone-melted quality, the highest concentration of any individual impurity being 15 ppm Al. The "prepurified" grade of nitrogen gas from Matheson Co. had a nominal nitrogen content of 99.996 pct. An "electrolytic" grade of hydrogen gas from National Cylinder Gas. CO. in which the principal impurity is water vapor was admixed with the nitrogen to prevent oxidation of these specimens. This grade was preferred to a purer grade because the presence of some oxygen helps in suppressing contamination of the specimens, for instance, by silicon from the porcelain furnace tube. EXPERIMENTAL PROCEDURE The specimens were equilibrated in vertical tube furnaces through which a 99 pct N2-1 pct H2 gas was passed at ambient pressure. For the 915", 918", and 999°C runs, a wound-resistance furnace was used, and for the 1217°C runs, a furnace with a tubular silicon carbide element was used. The temperature control system on both furnaces was similar: a Weston "Celectray" controller with a modulator, responding to the electromotive force of a thermocouple with its hot junction in the furnace, switched the furnace current between high and low settings. The temperature distributions in the working zones of the furnaces were determined with calibrated Pt/Pt-10 pct Rh thermocouples. The overall uncertainty in temperature was estimated to be ±3° at 915° to 999°C and ±5° at 1217°C . Consideration of the small temperature coefficients of the equilibria studied, together with the error limits in the method of analyzing for nitrogen, showed that further refinement in temperature uniformity would give no improvement in resultant accuracy. The reactive gas was generated by mixing together "prepurified" nitrogen and "electrolytic" hydrogen directly from cylinders commercially supplied. The flow rates of nitrogen and of hydrogen were fixed by setting with bleeders the pressure drops across the individual calibrated flow meters of constant resistance. For any given alloy, the solubility of nitrogen at 1-atm pressure (% N) was obtained from the analyzed nitrogen content of equilibrated specimens (% Na)according to Sieverts&apos; law, thus

Jan 1, 1962

By Thomas MacFarlane

IN smelting copper, lead, and silver ores, it is scarcely possible in every case to make analyses of the various parcels of ore, with the view of combining these and the fluxes so accurately as to yield, in the furnace, slags of exactly the most favorable composition. This is even more difficult with ores which require previous calcination, or with mattes which have been roasted in heaps. Even in cases where the greatest pains have been taken and the most elaborate calculations made beforehand, it frequently happens that variations in the working of the furnace interfere with the result so much desired. Generally, the practical metallurgist must be content with ascertaining the average composition of his ores and fluxes, making a calculation once for all as to the most advantageous mixture, and leaving slight changes in its composition to be taken care of as it is passing through the furnace. The various products then afford him the best material whereon to base his judgment as to the manner in which his smelting mixture is working. Of course the character of the slag is one of his chief guides, but it is not always possible from its outward characters alone to form a correct judgment as to its composition. Neither would it be possible or practicable to apply chemical analysis for this purpose, as it would be impossible to wait for its results while working a furnace. Abich was, I believe, the first to point out the relation existing between the composition of volcanic rocks and their densities, and to show that, the latter being ascertained, very correct conclusions

Jan 1, 1880