Search Documents

By L. W. Holm, A. K. Csaszar

A series of laboratory experiments was conducted in which oil was displaced from a porous medium by water-driven slugs of alcohols or similar solvents. The solvents used were soluble to some degree in both oil and water and covered the range of solubilities from complete solubility in oil to complete solubility in water. Displacement experiments were conducted on 2-and 3%-in. in diameter consolidated cores and 1-and 2-in. in diameter unconsolidated sand packs. The cores and sand packs ranged in length from 1 to 30 ft, and they were saturated with brine and crude or refined oils. The solvents used included ethyl alcohol, isopropyl alcohol (IPA), tertiary butyl alcohol (TBAI, secondary butyl alcohol (SBA), n-amyl alcohol (NAA), methyl ethyl ketone, acetone and others. It was found that all of the oil present in a porous medium could be miscibly displaced by injecting a slug of mutual solvent and driving it with water. The oil-recovery efficiency was dependent upon (1) the relative solubilities of the solvent in oil and water, and (2) the distance traversed by the flood. For complete oil recovery from cores, a smaller amount of a preferentially oil-soluble solvent was required, compared to the amount of preferentially water-soluble solvent needed. The size of the solvent slug required varied inversely with the linear flooding-path length raised to the 0.65 power. Water-driven dual solvent combinations (an oil-soluble solvent slug followed by a water-soluble solvent slug) were found to effect complete oil recovery with less total solvent than any single solvent used. In these dual-solvent displacement experiments, the slug size required varied inversely with length raised to the 0.55 power. Based upon the experimental results, a theory was developed to describe the displacement of oil and water by mutual solvents, and equations are presented to predict the production history in a linear system. These equations take into account the properties of the solvents and the porous medium. INTRODUCTION Oil-recovery processes which utilize displacing fluids that are miscible with the reservoir fluids have been studied extensively in recent years. Because of the poor contact efficiency and high pressure requirements of the LPG-gas displacement process there has been considerable interest in the alcohol-water process, and a number of studies have been made on the recovery of oil through the use of solvents which are mutually soluble in oil and water. An investigation by Sievert, Dew and Conleyl indicated that the use of mutual solvents would be limited because the presence of water in a porous medium would cause a phase break in the leading edge of the displacing solvent. Their study also showed that, in consolidated cores containing. only oil, the displacement of oil by a water-driven mutual-solvent slug of tertiary butyl alcohol (TBA) was affected by the viscosity ratios of the fluids involved. Gatlin and slobod3 concluded that an isopropyl alcohol (IPA) slug acts as a miscible piston, completely displacing both oil and water until the alcohol content of the mixing zone falls below the concentration necessary to maintain miscibility. Their study was conducted on uniform unconsolidated sand packs. They concluded further that IPA could be used effectively to recover oil from a watered-out sand. In a paper by Taber, Gamath and Reed4 relating an investigation on sandstone cores, it was stated that the displacement of oil by mutual solvents, particularly IPA, was not a miscible displacement and that no improvement in efficiency could be expected with increase in flooding-path length. However, their analytical analysis of the displacement mechanism using TBA is, in fact, one which indicates that the displacement is controlled by miscible mixing. They suggested that the lack of improvement in efficiency with flooding - path

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By Carle R. Hayward

THOUGH recent months have seen a rapid decline in lead-smelting activity and consequent uncertainty as to the future, the first half of the year showed progress in keeping with similar activity in other metals. Demand for scrap increased and various lead-bearing materials found their way to plants producing secondary lead. Some of these materials introduced complications into normal smelting procedure and were the cause of many conferences among plant officials attempting to find the most satisfactory method of treatment. If a blast furnace is to do itself justice it must be run with an open charge. Troubles inevitably result when materials are added to a charge which tighten it up and pre- vent free burning of the coke and con- sequent rapid smelting with a clean hearth This fact has long been recognized by plants producing primary lead, but only recently only it received the attention it deserves.

Jan 1, 1938

By W. D. Robertson, E. G. Grenier, V. F. Nole

The electrical, mechanical, and corrosion cracking properties of an age-hardenable Cu-Ni-Si alloy have been studied over a range of time, temperature, and deformation states for the purpose of determining the relationship between the properties and the structural state. The precifitate has been identi3ed as and the sites of preferred precipitation have been located by electron microscope studies of the structures developed by various combinations of heat treatment and plastic deformation. An extreme form of deformation banding has been observed in the aged alloy that results in high strain concentration in bands lying parallel to {111} planes. These bands are the structural paths along which transcrys-talline cracks propagate in the deformed alloy. The observations provide a basis for a general mechanism of transgranu-lar corrosion cracking of face-centered cubic alloys in terms of stacking fault probability. AMONG the age-hardening copper alloys the copper-nickel-silicon (Silnic Bronze) type is outstanding in exhibiting a high strength combined with a considerable capacity for cold working, a relatively high conductivity, and a low to negligible susceptibility to stress corrosion cracking. It is not a new alloy and it has been the subject of a number of investigations,1-5 which were made primarily to establish practical composition and heat treatment limits. The structural characteristics of the aging processes in this alloy have not previously been studied in detail. This particular investigation was undertaken to explore, in detail, and over a wide range of conditions, the properties obtainable by various combinations of working and heat treatment and to correlate structural changes with the observed mechanical, electrical and corrosion properties. MATERIAL AND PROCESSING Eight different commercial heats of the alloy were made and used in the investigation. The range of composition among the eight heats is shown in Table I. Billets, 8 by 24 in., were cast into water-cooled molds, extruded to 1.687-in. rod, and quenched in water after extrusion. Extruded material was rod rolled to 0.750 in., annealed at 1450° F for 2.5 hr, and quenched in water. Subsequent working operations were performed by tandem rolling to various sizes depending on the degree of reduction required. Final cold-working operations were performed by drawing to a uniform size of 0.187 in. diam and straightening by a roller straightening machine (Lewis). The combinations of heat treatment, working and aging that were investigated are summarized in Table 11; the various treatments were performed in the order given in each row of the table, and they will be subsequently identified by the symbols shown in the first column. SOLUTION TREATMENT All material investigated in the cold-worked condition, or cold worked prior to aging, was solution

Jan 1, 1962

One of the most unusual assignments in the his¬tory of Loffland Bros. Co. is now in progress with the drilling of a 72-in. diam. shaft in Nevada for the United States Atomic Energy Commission. Projected depth being 3200 ft, by volume, this is the same as a 216,672-ft hole 83/4 in. in diam. Every aspect of the operation is king-sized. The 15,000-lb bit moves into position over the well on a specially-made railroad car riding on rails 14 ft apart. The single drill collar weighs 300,000 lb, is 60 in. in diam., and 43 ft long. The drill pipe is 133/s-in. 72-in. N-80 casing fabricated with special tool joints. The bit chews up 1.05 cu yd of rock for every ft of penetration (This is equal to the volume of 67.71 ft of 83/4-in. hole.

Jan 9, 1964

By W. H. Holman, J. B. Wagstaff

IN spite of considerable interest among blast furnace operators on the question of the penetration of air into the furnace, there is still uncertainty as to how far the blast does, in fact, penetrate. Moreover, it is not always clear just what is meant by the word penetration in this sense. In 1952, Elliott et al.1 showed that at the end of each tuyere of a blast furnace there is more or less of a void. In this region, coke particles are blown around by the force of the air. This explained the well-known observation reported by Sweetser2 hat if a bar is pushed into a furnace through a tuyere it will go easily into the furnace a distance of some

Jan 1, 1958

By Gerald Edmunds

CASTINGS of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, some-times nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is devel-oped to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and there-fore the position of the grains is more com-plex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicat-ing that thermal contact was better there than in neighboring areas.

Jan 1, 1940

By H. C. Fiedler

A high degree of cuhe-on-edge grain orientation and good magnetic properties were obtained in Si-Fe strip processed from laboratory heats containing vanadium nitride inclusions. The higher the nitrogen content the greater was the restraint on normal grain growth and the greater was the ability to undergo secondary recrystal-lization. The degree of restraint in a heat containing magnanese sulfide inclusions was slightly greater than that in the lowest nitrogen vanadium nitride heat. The high rate of diffusion of nitrogen in the temperature range in which the texture is developed makes it necessary to retard the loss of the inclusions until the texture has been developed. MAY and Turnbulll have shown that to develop the cube-on-edge secondary recrystallization texture in Si-Fe it is necessary that inclusions, such as manganese sulfide, be present to prevent normal grain growth. They showed that the driving force for the growth of the secondary grains is inversely proportional to the diameter of the matrix grains, and that the function of the inclusions is to maintain a small matrix grain size. Fast3has developed cube-on- edge texture in Si-Fe by nitriding the hot rolled band. The silicon nitride thereby formed promotes secondary recrystallization during the anneal of the final gage strip. To obtain the best magnetic properties, the inclusions must be removed from the strip after the grain orientation has been developed. Nitride inclusions have an inherent advantage over sulfide inclusions in that the greater diffusivity of nitrogen as comared to sulfur permits the use of shorter times and or lower temperatures for the purification heat treatment. The purpose of the work to be described was to examine the usefulness of vanadium nitride inclusions in developing the cube-on-edge texture and to determine the magnetic properties of oriented strip made from heats containing these inclusions. A comparison is made with a heat having had iden-

Jan 1, 1962

By R. J. Brison, R. D. MacDonald

This chapter is written primarily from the standpoint of development of flotation processes for treatment of specific ores. However, most of the principles and techniques discussed are equally applicable to other forms of applied flotation research such as improvement of procedures in existing plants and development of new reagents or methods without reference to specific ores. Because it is not possible to cover this subject in detail here, much of the material presented is in the form of a guide to the literature, with emphasis on readily available, English language publications. Details are included only if considered to be widely applicable or not readily accessible in the literature. Related subjects which are covered elsewhere in this volume, such as flowsheet design and statistical techniques, are not emphasized in this chapter. The material presented is intended primarily for those familiar with the theory and practice of flotation, but with limited experience in applied flotation research. It may be of value to the experienced investigator as well, by calling to his attention some useful viewpoints or techniques that he may have overlooked. It has often been said that flotation is more of an art than a science. In- deed much of the knowledge of flotation behavior is empirical. However, the unsystematic, artisan approach to flotation problems results only in an ac- cumulation of unrelated data. Like any other physical or chemical process, flotation is amenable to investigation by systematic experimental methods. The experiments should be based, as far as possible, on an understanding of the natural laws that govern the process and on good experimental procedures. SAMPLING OF A DEPOSIT In working out a flotation process for a mineral deposit, no step is more important than that of obtaining a suitable sample or samples. Experimental procedures cannot compensate for the lack of a representative sample. Methods of sampling a deposit have been published elsewhere,l-4 but a few points are of special importance from the standpoint of flotation. First, the sample should be representative of the deposit, not only in respect to chemical composition, but also in respect to mineralogical composition and degree of dissemination of the valuable minerals. To help ensure

Jan 1, 1962

By Wm. A. Haven

As soon as the likelihood of American participation in the war was established, and in spite of the fact that we can produce almost as much as all other countries combined, the demand for prompt deliveries of iron and steel products from American factories began to exceed their utmost capacity, and, after fifteen months of practically full operation, has continued to do so. Therefore, it would seem worth while to review some of the aspects of the supply and demand for steel as well as the efforts that are being made to bring them into balance. It is still being debated as to whether the situation should be defined as a real shortage that will persist through the emergency period or as a temporary one than can be relieved by less drastic measures than a Government-sponsored program of expanding existing plants and building new ones.

Jan 1, 1942

By P. D. Frost, H. A. Robinson, J. R. Doig, M. W. Mote

The mechanism of hardening in heat-treatable zirconium alloys was foUNd to be analogous to that for titanium alloys. Zirconium containing a relatively large addition of a ß -stabilizing element such as molybdenum or columbium can be hardened by the following transformation: Lean alloys, having insufficient alloy content to retain ß at room temperature are hardened by the following transformation: Application of these findings in Zr-Mo-Sn and Zr-Nb-Sn alloys produced strengths as high as 190,000 psi with reasonable ductility. PRIOR research on zirconium alloys has been concerned with development of greater strengths and creep resistance by solid-solution hardening or by dispersion hardening. Although solution and aging heat treatments had been applied earlier to zirconium alloys, quenching frequently produced low ductility. The possibility that the ß-to-w transformation, discovered earlier in titanium alloys,' might also occur in zirconium alloys and cause low ductility was considered, and, indeed, was found as predicted2 to be the case. In the earliest experiments, the heat-treatment response of titanium, too, was disappointing. However, by avoiding the formation of the embrittling w phase, it became practical to obtain room-temperature strengths higher than 180,000 psi, with elongation values of 10 pct.3 Based on the present concept of titanium heat treatment, the principal requirement for a heat-treatable zirconium alloy is that it contains a certain minimum amount of one or more ß -stabilizing elements. Only molybdenum, columbium, and tantalum, when present in sufficient amounts, are known to stabilize ß zirconium to room temperature during rapid cooling from the ß field. Tantalum was undesirable because of its high thermal-neutron cross section. Aluminum and tin are effective a stabilizers, but aluminum has been shown to seriously decrease the corrosion resistance of simple zirconium alloys in hot water. Therefore, for the present study, tin was used as the stabilizer addition. The alloys selected for this evaluation are presented in Table 1 along with their analyses and ß-transus temperatures. The analyses indicated that intended compositions were usually realized. EXPERIMENTAL PROCEDURES All of the alloys were melted from sponge zirconium and fabricated to sheet for heat treatment

Jan 1, 1960

Jan 1, 1964

By B. C. Riblet

THE president of a large smelting and refining company once telegraphed me that they had acquired extensive mining interests in northern Peru and requested me to inspect their properties as it would be necessary to install a system of aerial tramways between their mines and treatment plant. The concentrator was about 50 mi. from the coast, reached by a fairly good motor road. From the concentrator an aerial tramway would he required, about 6 mi. long, to their first property, a gold and silver mine. The lower terminal of the tramway was at an elevation of 4000 ft. and the mine at an elevation of 9500 ft.

Jan 1, 1937

By AIME AIME

NAPOLEON'S dictum that an Army travels on its stomach has not changed in this present war, but the things an Army's stomach calls for would be more than strange to Napoleon. Today one of the main articles of diet for the mechanized army is oil and gasoline, and the chief and most efficient source of 'apply overland is the pipe line. It was a flexible 4-in. pipe line that supplied the voracious appetite of tanks, trucks, jeeps, and planes across the North African desert. and it is the 1800-mile pipe line from Calcutta to Kunming, Yunnan Province in China, the longest in the world, that supplied oil and 100-octane gas for the trucks, tanks, Jeeps, and planes fighting on the Assam-Burma-China front in recent months. Completion of this approximately 1800-mile pipe line to China over rivers that had never been bridged, over hill that towered 9000 ft., and over swamps

Jan 1, 1945

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature microhardness of as-grown and annealed MoaC single crystals was measured on the (0001), {2110), and1012) planes using Knoop and Vickevs indenters at loads ranging front 25 to 1000 g. The orientatimz dependence of hardness with respect to crystal axes was also studied. The average random hardness of as-grown crystals was determined to be 1520 kg per sq nm. Annealing to 2000°C decreased. the average hardness by 150 units. An increase in hardness after annealing at 2200 ;C was noted. Optical and electron microscopy revealed slip and twin traces on all planes studied, as produced by mi-cvohavdness indentations. Basal (0001)(2i10) slip was determined to be the primary slip system and was substantiated by electron transmission microscopy. A secondary {1010)(2110) slip was produced by mi-crohardness indentations. The lattev also produced twinning- of the {10i2)[0001] type, as proven by electron diffraction. Electrical resistivity and elastic-modulus anisotropy were found and correlated with hardness anisotropy and Mo2C crystal structure. Elastic-modulus values were obtained by microhard-uess and ullrasonic methods. Bonding mechanism of Mo2C is discussed. ROOM-TEMPERATURE microhardness indentations are useful for studying hardness anisotropy, slip, and twinning in brittle materials. Slip has previously been produced in this manner in and WS~~.~ Recently, the authors5 reported slip of the {10i0)(11~0) type produced by high pressure and microhardness indentations on hexagonal TiBz (c/a = 1.066) single and polycrystals. This slip system was also reported by French and ~homas' and Taka-hashi and ~reise~ for hexagonal WC (c/a = 0.976) crystals. These results suggest that prismatic rather than basal slip is favored in hexagonal nonmetallic materials having a c/a ratio considerably less than the ideal (1.633). Buerger precession and cylindrical X-ray rotation patterns were previously' taken on cleaved sections of the Mo2C single crystals studied in this work. Th~y were found to be hexagonal MoaC with a. = 3.0233A, co = 4.7344A, and C/O = 1.5660. The latter ratio is close to that of the beryllium metal (c/a = 1.57), which slips primarily on the (0001) plane: but also slips on the (1010) planes.'0 ~irconium" (c/u = 1.59) and titanium12 (c/o = 1.59) deform mainly by slip on nonbasal planes which contain a close-packed direction. This is due to the fact that for these two metals the initial resolved shear stress for slip on the (10i0) prismatic planes is lower than that on the (0001) plane. The prominence of basal rather than prismatic slip in metals of high c/o ratios is shown by cadmium (c/a = 1.89), zinc (c/a = 1.86), and magnesium (c/a = 1.62) which deform mainly by basal slip. However, in case of the latter, by stressing magnesium crystals in tension or compression parallel to the basal plane, slip on (10i0) planes can also be produced.13 Several hardness values for polycrystalline Mo2C are reported in the literature: Biickle ' and Samsonov'~ give a value of 1800 and 1479 kg per sq mm, respectively, at a 100-g load; and Kieffer and Benesovsk~'~ report a value of 1950 kg per sq mm at a 50-g load. ~ott'~ reports a Vickers hardness value of 2000 kg per sq mm, with the load unspecified. A Rockwell A hardness value of RA = 88 has also been reported.'' In the present work, for comparison with single-crystal Mo2C hardness values, a Khnloo value of 1600 It 150 kg per sq mm was found on 99.6 pct pure and 99 pct dense hot-pressed Mo2C. This work was undertaken partly to explain the considerable differences in hardness values reported for polycrystalline Mo2C. EXPERIMENTAL The Mo2C single crystals investigated were prepared by a Verneuil-type process using an electric arc by the Linde Co. of the Union Carbide Corp.lg The largest specimens grown were boules 7 mm in diam by 40 mm in length. The crystals had an average density of 9.04 g per cu cm, with a Mo + C content of 99.8 wt pct. The major impurities were: 100 ppm each Na, Zr, and Ca; 85 ppm 0, 55 ppm Fe, and 10 ppm each Cr and Ta. The crystals were found to be carbon-poor, the average carbon content being 5.73 wt pct (stoichiometric value is 5.89 pct). The molybdenum content was found to be 94.08 pct, which is nearly stoichiometric. Electron-microprobe traverses of selected specimens were done with a Phillips-AMR microanalyzer. Thin-film and carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to optical and electron-optical studies, specimens were mounted in Lucite and polished on a vibratory polisher using diamond-paste grades ranging from 9-1 p and Linde A powder for up to 48 hr. Dilute nitric acid was used for thin-section polishing and chemical etching for 1-15 min. Electrical-resistivity measurements at room temperature were taken with a Rubicon bridge, using gold contacts. For hardness measurements, a Tukon Microhardness Tester Type FB with Knoop and Vickers indenters was used. Measurements were taken at loads ranging from 25 to 1000 g; however, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Indentations of cracking classes 1 and 2 only were considered for hardness determinations.20)21 (There are six cracking classes, ranging from "class 1" for a perfect inden-

Jan 1, 1967

By D. L. Harris, A. M. Gaudin

Observations were made of the distribution of mercaptan containing S35 between aqueous solution and mineral and between aqueous solution and the gaseous phase. Although equilibrium may not have been attained, adsorption of the reagent was shown to occur reasily from air or aqueous solution on sphalerite, zincite, and willem-ite and to correspond to flotation. Adsorption on quartz did not similarly occur. THE following results, presented here in condensed form,' were obtained in a preliminary study of the adsorption of n-hexane thiol, hexyl mercaptan, on sphalerite, zincite, willemite, and quartz, from aqueous solution and from a gas. Interest in this subject was aroused by a Belgian report' of effective use of hexyl mercaptan for flotation collection of oxidized zinc minerals. The relatively low boiling point, 149°C, of the mercaptan3 suggested the desirability of extending the usual measurements of partition of collector between aqueous solution and gas and between gas and mineral. It is believed that this paper presents the first measurements of this type on a flotation system. Attempts were made to carry out the measurements at equilibrium, but as the work progressed it became increasingly doubtful that this desirable condition had been achieved. To control composition and extent of the gas phase, the apparatus was a wholly-enclosed thermally-controlled glass system. Because of these constraints and the desirability of dealing with pure minerals, a scale of operations was chosen in which a few grams of deslimed mineral were used in each test. It was also necessary to choose a particularly sensitive method for mercaptan analysis, and in fact a method that would permit the experimenters to follow the approach to equilibrium. For these reasons mercaptan marked by radiosulphur 35 was used. An analysis was made for the radiosulphur by a modification of the method of Gaudin and Carr. Coarsely-crystallized sphalerite was handpicked, stage-crushed in the dry state, wet-screened on a 200-mesh sieve, and deslimed in water at about 5 microns. Further treatment consisted of a wash in dilute aqueous hydrogen peroxide, drying, removal of the dark-colored fraction in a Frantz magnetic separator, washing in very dilute hydrochloric acid, repeated washing in distilled and conductivity water, and drying. The last washings showed a conductivity equivalent to a few ppm NaC1, that is, much more than would be provided, theoretically, by a saturated ZnS solution. The material was stored dry in sealed bottles. Analyses were as follows: Zn, 62.3 pct; Fe, 0.43 pct; Cd, 0.44 pct; S, 31.2 pct; Mn, 0.001 pct. The specific surface (BET method) was 2000 cm2/g. Zincite from Franklin furnace of the New Jersey Zinc Co. was hand-picked, dry-crushed, wet-screened at 100 mesh, and deslimed at about 10 microns. After drying, the associated zinc, manganese, calcium, and silicate minerals were removed in a Frantz magnetic separator. The purified zincite was washed in distilled water and conductivity water to a conductance of less than 2 ppm equivalent NaC1, dried, and stored. Analyses were as follows: Zn, 75.1 pct; Fe, 0.9 pct; Mn, 2.78 pct. The specific surface (BET method) was 1740 cm 2/g. Willemite, also from Franklin furnace, was purified similarly. Analyses were as follows: Zn, 52.5 pct; Fe, 0.12 pct; SiO², 27.3 pct; loss on ignition, 0.13 pct. The specific surface was 1760 cm 2/g. Conductivity water (double-distilled) and demin-eralized-distilled water were used in most of the tests. The specific resistance was not less than 600, 000 ohms, and usually above 1,000,000. Radiosulphur-marked hexyl mercaptan (1-hexane thiol) was synthesized by Tracerlab, Inc., Boston. Two lots were secured several months apart. The last lot, consisting of about 0.5 g of the mercaptan, had a total activity of about 10 millicuries. Tracerlab Co. guaranteed only the activity; hence a quasi -vapor pressure determination (based upon an S analysis) of the mercaptan was made. The calculated value, 4.2 mm of mercury at 25.5' C, has been compared with that of a sample of Highest Purity 1-hexane thiol from Fisher Scientific Co. The latter had a vapor pressure of 4.5 mm of mercury at 2.5 C. Analytical Procedures The sample containing radiosulphur-marked mercaptan was oxidized to convert the mercaptan sulphur to sulphate, carrier barium sulphate being added to provide a suitable quantity of total barium sulphate in a filter cake. The precipitate was filtered and dried, and counting was carried out either in a streaming-gas (Q-gas) counter for high sensitivity or with an end-window G-M counter for convenience. The oxidized and precipitated mercaptan gave a radioactive count of 65 counts per minute per microgram in the end-window Geiger-Mueller counter and 1100 counts per minute per microgram in a Q-gas counter. For standardization of the mercaptan solution, 15 replicate analyses were made. The average deviation per measurement was about 1600 cpm in 65,000 cpm, the probable error in the mean being 275 cpm. It

Jan 1, 1955

By R. H. SWEETSERS

A Discussion of Mr. Hall's paper, read at the Washington Meeting, February, 1905. R. H. SWEETSER, Sault Ste. Marie, Ont. (communication to the Secretary*) :-The recent work of furnace No. 1 of The Algoma Steel Co., at Sault Ste. Marie, Ontario, using for fuel, first all charcoal, then a mixture of charcoal and coke, and finally all coke, upsets the estimates given by Mr. Hall in the last two paragraphs of his interesting paper. Furnace No. 1 was built for a charcoal-furnace, and it was run on charcoal fuel from March 6 until July 9, 1905; then, for a week, a mix¬ture of charcoal and coke was used, and, since then, coke alone has been the only fuel. It is to be regretted that at no time, during the run on charcoal, was there enough charcoal on hand and " in sight'" to warrant blowing the furnace as hard as it should have been blown. During April and May the supply of charcoal limited the amount of blast to about 8,000 cu. ft. of air per min.; in June, to about 8,900 cubic feet. For a few days in July about 10,000 cu. ft. were blown, and then the maximum daily output, 173 tons (2,240 1b.), was reached. At all times the quality of the charcoal was poor, having been made from wood cut from three to four years before. Doubtless this furnace could have produced .200 tons of iron per day, even with this quality of charcoal, provided the supply had been sufficient; and with good charcoal I see no reason why it could not make as much iron per day as it has made with coke. During the one week of using a mixture of charcoal and coke, the changes in quantity of blast and composition of the slag followed each other so closely that no single condition could last long on the furnace. The results were good, and the pig-iron was about the same in quality as that made during the

Jan 1, 1906

By A. C. Fieldner, W. A. Selvig

For purposes of coal classification it is desirable to know the composition and calorific value of the pure coal substance; that is, of the coal free from its ash-forming minerals. Two methods suggest themselves: (1) To free the coal from most of the ash-forming material previous to the analysis; and (2) to analyze the coal as received and calculate the analysis, with certain more or less arbitrary corrections, to the pure-coal basis. Calculation methods are obviously more apt to give correct results with low-ash than high-ash coals. With coals of unusually high ash it would appear preferable to remove, previous to the analysis, as much of the inorganic matter as possible, by float-and-sink or acid-treating methods. Effect of Ignition on Inorganic Constituents of Coal The need of corrections in calculating analysis to the pure-coal basis is due to the fact that the ash, as determined by ignition, is not the same, in either weight or composition, as the inorganic mineral matter in the coal. On ignition a number of changes occur in the coal such as loss of water of hydration of the shaly material, conversion of pyrite (FeS2) to ferric oxide (Fe203) with evolution of the sulfur as sulfur dioxide or possible fixation of more or less of the sulfur in the ash as calcium sulfate (CaSO4), and decomposition of calcite (CaC03) to calcium oxide (CaO). The amount of sulfur from pyrite which remains in the ash as calcium sulfate depends on the amount of calcite and pyrite in the coal. Certain coals high in both calcite and pyrite show relatively large amounts of sulfate sulfur in the coal ash. The determination of total carbon and hydrogen in coal includes, besides the organic carbon and hydrogen, the carbon of inorganic carbonates such as calcite, and the hydrogen of the water of composition of some of the ash-forming minerals. For detailed discussion of corrections proposed for calculations of coal analyses to the " pure "

Jan 1, 1930

VITRIOL is likewise a mineral substance from whose exhalation, according to the opinion of some, are generated and produced the elemental materials or substances which produce metals, particularly gold. It is not a fumosity from metal nor is it a thing from which metal is extracted in any manner, although it shows in certain ways that it is not entirely without metal since it produces a certain trace of it. It is a thing that has a great resemblance to alum; it has a biting substance, is sharp to the taste and pungent to the tongue, and has an astringent nature. It dissolves in water and every damp place in a short time. They say that the reason for this lies, as with every other mineral, in its poorly joined watery substances. Nor does this mean that it does not contain much earthiness; on the contrary it seems to me that there are in it five. [2.9v] different participating qualities, that is, the property of sulphur, the action of alum, the corrosion of niter or of salt, and from the metals, the properties of copper and of iron. Its ore is mined in the valleys of mountains in wild but not too rugged places. It is more a gray earth or soft dead rock than a hard stone. It always has in it some yellow and green spots or near it is some sulphur mineral, either large or small.. When it is beneath the earth it exhales a sharp and very strong foul odor of scorching similar to that of sulphur. And the waters that rise where it is are all foul, earthy, and thick, some boiling with great fumes and others without great fumes, so that they surely appear to be infernal products in many places where there is a large quantity of it. After you have excavated and sorted well the quantity you wish, the ore must be put in a heap in open airy places before the vitriol can be extracted from this soil or ore, however you wish to call it. And it is left thus exposed to the weathering of the rains, the cold, and the sun for five or six months. It must be turned several times in order to bring to the surface that which was underneath; and always when this is done it is broken small with the eye of a mattock so that it is better heated and baked throughout. When it has been brought to this point it is covered over by a shed built above it or it is carried under a hut that has already been made. Here it is left to stand for another six or eight months before it is worked.

Jan 1, 1942

By C. G. Dunn

Identification of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereo-graphic projection with one pole per orientation.' However, accurate data based on calculations of the positions of all {1001 planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. Method of Computing Orientation OF a Twin It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given in terms of two angle variables, two sets of which appear in the following equations: Polar Net Wulff Net x = , sin ?p cos Fbp x = r COS ?w y = r sin ?p sin Fp y = r sin ?w cos Fw % = r cos ?p z = r sin ?w, sin +, The three numbers z, y and z determine a length r as well as a direction (0, 4) in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 + L2)1/2, where h, k and I are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {Ioo} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3,4' Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A' being one of the four {112} or {III} type* first-order twills of S. The orientation of S—i.e., the positions of poles of (I00)

Jan 1, 1945