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By Martin F. Littmann

Inclusions of MnS and Fe3C have been introduced into single crystals of 3 pct Si-Fe to study their effects on recrystallization behavior and textures after cold rolling and annealing. The presence of MnS in (110) [001] and (111)[112] crystals inhibited primary grain growth and promoted secondary recrystallization but did not alter the texture significantly after annealing at 1200°C. The presence of Fe3C in (llO)[OOl] and (100)[001] crystals caused a refinement of the primary re crystallized grain size but did not promote secondary recrystallization. THE texture behavior of single crystals of 3 pct Si-Fe during deformation and recrystallization has been studied by numerous investigators. The early work of Dunn&apos; followed by Decker and Harker2 involved relatively small cold reductions. More detailed studies of Dunn3&apos;4 and of Dunn and Koh5&apos;6 involved a reduction of 70 pct and recrystallization at 980°C for several crystals. Walter and Hibbard7 studied a greater variety of initial orientations and sought to relate the textures to those of polycrystalline material. Attention was focused on the nucleation process during early stages of annealing and on surface energy effects in studies by Walter and Dunn8 and by HU.9&apos;10 One of the most extensive investigations has been reported by T. Taoka, E. Furubayashi, and S. Takeuchi.11 Most of this work has been conducted using relatively pure crystals with minimal amounts of precipi-tate-forming elements such as carbon, oxygen, sulfur, and nitrogen. Recently, however, S. Taguchi and A. Sakakura have observed that AIN precipitates can alter the recrystallization textures of rolled (100)[001] crystals.12 The present studies were initiated to determine effects of MnS and Fe3C precipitates on recrystalli-zation and grain growth behavior of rolled single-crystals of 3 pct Si-Fe. Both of these types of inclusions play significant roles in the recrystallization behavior leading to the formation of the (110)[001] or cube-on-edge texture in commercial grain-oriented silicon iron. It is well known that (110)[001] primary grains are formed by recrystallization of (110)[001] or (11 l)[ 112] crystals after cold reduction of about 60 pct or more. Crystals of these orientations, therefore, were selected for study of the effect of MnS in-clusions on grain growth. On the other hand, a major component of the texture of cold-rolled, polycrystal-line 3 pct Si-Fe is the (100)[011] orientation. The function of Fe3,C inclusions is of interest for this orientation. EXPERIMENTAL PROCEDURE The single crystals used are listed in Table I and were obtained from commercial Si-Fe alloy processed to produce (110)[001] and (100)[001] texture by secondary growth. The cube-on-edge material was 0.59 mm thick. Suitably large (110)[001] crystals 25 mm wide were selected and their orientations were determined using an optical goniometer. Etch pits for texture determination were formed by a ferric sulfate solution. The other crystals used in the study with (100)[001], (100)[011], and (111)[112] orientations were obtained from sheet which contained large grains developed from secondary recrystallization by a surface-energy driving force.13 Most crystals had a (100) plane very nearly parallel to the sheet surface and the rolling direction could be selected readily. The same sheet also contained a few crystals with (111) planes parallel to the sheet surface, these also being a result of growth by surface energy. The crystals selected from the sheet were about 25 mm wide and 0.25 to 0.28 mm thick. As shown in Table 11, the crystals already contained about 0.070 to 0.10 pct Mn. Inclusions of MnS were incorporated into crystal 36 in the following manner. The crystals were first sulfurized by holding them Table I. Initial Orientations of Crystals Crystal No. Initial Orientation Thickness, mm Special Treatment 34 (I10) [00l]* 0.59 None 36s (110) [001] 0.59 Sulfide precipitates added 30,40 (111)[Ti21 0.28 None 43s (III) [Ti21 0.28 Sulfide precipitates added 37 (100) [Oll] 0.30 None 37C (100) [01I] 0.27 Carbon added 41 (100) (01I] 0.25 None 41C (100) [OI11 025 Carbide precipitates added 42 (100) [OOl] 0.25 None 42C (100) [001] 0.25 Carbide precipitates added *Tilted 4 deg to r~ght about R.D. Table II. Compositions of Crystals Special Treatments Base Analysis ~ ______________________£________________Crys- Crystals Pct Si Pct C Pct Mn Pct S Pct N Pct Al tal Pct C Pct S 34.36 2.93 • 0.099 <0.005 - 0.0014 36S 0.011 30.37 to 42 2.78 0.0057 0.070 0.001 0.0008 0.0011 43S 0.022 37C 0.029 -41C 0.028 -42C 0.026 *Estimate 0.004 pct. Oxygen estimated <0.003 pct on all samples

Jan 1, 1970

By T. Sterry Hunt

Jan 1, 1882

By Gerhard Derge, Harold Markus

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Harold Markus, Gerhard Derge

The first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from 1.12† volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. Experimental Data Cations.—The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.1 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 10-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

Mar. 3-7, ASTM, spring meeting and commitee week, Hotel Statler, Cleveland. Mar. 4, AIME, Morenci Sub-Section, Longfellow Inn, Morenci, Ariz. Mar. 5, AIME, Chicago Section, Ladies Night, Chicago. Mar. 10-13, National Electrical Mfrs. Assn., spring meeting, Chicago. Mar. 10-14, National Assn. of Corrosion En-Engineers, annual convention, Galveston. Mar. 11, Society for Applied Spectroscopy, 6 pm, supper, Tosca&apos;s; S pro, meeting, Socony-Vacuum Training Center, 63 Park Row, New York. Mar. 16-19, American Institute of. Chemical Engineers, Atlanta Biltmore Hotel, Atlanta. &apos;Mar. 17-21, ASTE, annual meeting, Chicago. Mar. 20, AIME, Philadelphia Section, Engineering Bldg., University of Pennsylvania, Philadelphia. Mar. 22-Apr. 6, Chicago International Trade Fair, Navy Pier, Chicago. Apr. 1, Society for Applied Spectroscopy, Socony-Vacuum Training Center, 63 Park Row, New York.

Jan 1, 1952

By S. D. Michaelson

[CONTENTS PACE See TP 2377, Min. Tech, May 1948 for discussion of A Technique for Photographing Difficult Subjects through a Petrographic Microscope (TP 2092 by DONALD W. SCOTT, Min. Tech., Nov. 1946. Discussion by HORACE WINCHELL). Metallurgical Efficiency-a Yardstick in Lead-zinc Flotation Metallurgy (TP 2141 by R. A. ....... PALLANCH, Min. Tech:, March 1947. Discussion by S. D. MICHAELSON). I Symposium on Milling Devices and Practices. (TP 2162 by J. F. MYERS and R. J. TOWER, Min. Tech., May 1947. Discussion by HARLOWE HARDINGE). ............ 2 Rod Milling-Plant and Laboratory Data. (TP 2175 by J. F. MYERS, S. D. MICHAELSON and F. C. BOND, Min. Tech., July 1947. Authors&apos; supplement and discussion by HARLOWE .......................... HARDINGE, and B. H. IRWIN) 2 A New Separating Vessel for Sink-float Concentration. (TP 2182 by E. C. BITZER, Min. Tech., May 1947. Discussion by E. H. CRABTREE, JR.) .................. 5] Metallurgical Efficiency-a Yardstick in Lead-zinc Flotation Metallurgy S. D, MICHAELSON*-The method of determining the efficacy of a separation described in this paper, gives the metallurgist a most useful guide for keeping his ship on an even keel When the ore Waves vary from placid seas to high breakers. Now that such a method of evaluating metallurgical efficiency has been developed and proven practical, it Would seem logical to introduce the next, and more final, factor of Economic Efficiency. I choose to define this term as the percentage ratio of net return from milling to the theoretical maximum net return. The actual operating cost subtracted from the actual mill return represents the net actual amount received for the material treated. Experienced operators of most plants Would ordinarily have enough data on hand to estimate a theoretical milling cost per ton, based on labor, power, supplies and maintenance When operating at maximum tonnage With minimum trouble and under ideal ore conditions. When this theoretical estimated cost is subtracted from the theoretical maximum ore return (calculated by Pallanch&apos;s method) the resulting figure is the maximum theoretical net amount the mill operator could hope to realize in processing the ore. The percentage ratio of these sums, of actual to theoretical, is the economic efficiency of the operations. This economic efficiency, if determined on the basis of a fixed market price for metal and similarly fixed base rates for labor, power and supplies, Will reflect the effect of changes in milling practice, labor efficiency and equipment condition. When computations made on the basis of actual current rates for labor, power and supplies are compared With similar actual figures for past periods they will show forcefully how energetic our hunt must be to develop man saving controls, more effective metallurgy, and better equipment to maintain profitable operations. Such computations also offer a simple means of determining how much more labor, supplies and power can be put into the mill operation to obtain an increase in metallurgical recovery at a profit.

Jan 1, 1947

By B. R. Hollebone

The chemical action of molten anhydrous pyridinium chloride (pyridine hydrochloride) on oxy salts and ores of some Group IV and V metals are discussed-in particular zirconium, hafnium, niobium (columbium) , and tantalum. Laboratory-scale experiments are described whose results suggest that this reaction might provide a practicable means of converting ores of these metals to the anhydrous metal chlorides. Experimental results are given which provide some insight into the nature of the reactions and some of the compounds which could be present at intermediate stages. The treatment of ores of the more refractory metals is difficult and expensive and often demands the use of gaseous chlorine, hydrogen fluoride, or other reagents which are, if nothing else, expensive and dangerous to use. This situation is, of course, due to the strong metal-oxygen affinity resulting from the high charge and the small size of the metal ion which combine to produce such high lattice energy in the metal oxide as to defeat standard reduction methods. Thus, the characteristic of these metals which leads to one of their most important properties—corrosion resistance—is the main hurdle in obtaining the metal. Many common methods&apos; for treating ores of zirconium and niobium (columbium), for example, proceed as directly as possible to the preparation of anhydrous halides. These halides are purified by now standard processes of solvent extraction, fractional distillation, and so on. This paper reports on preliminary stages in the development of a method of treating these ores—particularly of niobium—so as to prepare the anhydrous, volatile halides by the use of chemical reagents which are much more easily handled than those used at present. CHEMICAL PRINCIPLES The solvent action of aminium halides has been referred to periodically in the literature over several decades. The chemistry of pyridinium chloride has been discussed particularly by Audreith2 and Starke.3 However, since this is not familiar chemistry in its nonaqueous setting, it is perhaps well to point out some general metallurgical principles and applications. One can use, as point of departure, the fact that HC1 dissolved in pyridine is an acid very much the same as aqueous HC1. It thus gives essentially all the reactions of the HC1 with which we are familiar. However, when the ratio of HC1:pyridine reaches 1:l (a ratio far higher than is possible with H2O) the solution becomes solid C5F5NHC1, pyridinium chloride.* Inter- estingly, the acidic properties of HC1 persist in this medium, although they are manifest only in the molten state of the compound. Some typical reactions of divalent metal compounds which we have carried out in our laboratories are the following: 2PyHCl + Zn — (ZnCl2) + H2 + 2Py 2PyHCl + MnO — (MnCl2) + H2O + 2Py 2PyHCl + CuS — (CuCl2) + H2S + 2Py 2PyHCl + CaCO3 — (CaCl2) + H2O + CO2 + 2Py In these equations, the parentheses indicate a solvated compound which in water would be predominantly a hydra ted cation but which in molten PyHCl will more likely be a complex chloro-anion of the type MC14-. Some important physical properties of pyridinium chloride (PyHCl) are given in Table I. One sees from the data in Table I that at the temperature of molten pyridinium chloride both water and pyridine will boil away. Thus the system will be kept anhydrous. For this reason the reaction 2NbCl5 + 5H2O— Nb2O5 + 10HC1 has no counterpart in molten PyHCl. Instead, the chloride is made even more stable by the formation of a hexachloro complex: Nb2O5 + 12PyHC1 — 2PyHNbC16 + 5H2O + 10Py One interesting property of these complexes is their thermal instability which for the case of niobium can be illustrated as PyHNbCl6 — PyHCl + NbCl5 With a view to possible use of this chemistry in ore treatment, we have attempted to dissolve Pyrochlore (essentially FeO - Nb2O5) and recover the NbC15 from it.

Jan 1, 1968

By J. H. Anderson, G. A. Parks, B. K. Jindal

Both temperature and humidity are important variables in electrical separations. By independent control of temperature and water vapor pressure, it is shown that charge depends primarily upon relative humidity, not on temperature or water pressure alone. All the effects of temperature changes other than modification of humidity are apparently small. However, humidity control can be achieved through manipulation of the more tractable variable, temperature. Both temperature and humidity are important variables in electrical separations. Some of their effects have been described in general by Fraas1,2 and by Ralston.3 The influence of temperature and humidity may be considered a problem in industrial separations because humidity, especially, is not normally controlled, hence leads to unpredicted quality control problems. The problem is significant whether the separation is based on conductivity differences or on contact electrification. There is no doubt that water adsorbs from humid atmospheres onto mineral surfaces resulting in conductivity changes.&apos;-8 An empirical relationship between conductivity and humidity is1.4-6,8 where a and b are constants peculiar to the substrate, and s and h are the conductivity and relative humidity respectively. Some authors have taken advantage of differences in a and b among minerals to make or propose electrodynamic separations in which h is the key control variable. Fraasl,2 reported that the charge developed on quartz and feldspar through contact with aluminum is sensitive to humidity, as illustrated schematically in Fig. 1. Lawver9 found that the charge developed by quartz on contact with several materials was tem-

Jan 1, 1967

By Cushwa, C. C.

AT the Park Utah Mine, labor costs of stoping A have been reduced from 30 to 40 per cent. by the use of double-drum hoists and scrapers. The application of scrapers varies with the methods of timbering. In stopes, which must be timbered with square-sets or stringer sets, one method is used; another is used in wide orebodies that can be held open until filling is introduced; and still another in narrow flat veins. Nearly all the oreshoots at the Park Utah lie at less than 50" from the horizontal, and most of the ore is difficult to handle through flat chutes. Proper care is probably the most important requisite for successful scraping, as serviceable equipment can be obtained from several manufacturers. One capable mechanic, therefore, was put in charge of the scraper hoists. He visits every stope daily, oiling hoists and tail1 blocks, inspects all equipment, splices cables and changes "set-ups" when necessary; his pay has been a good investment. The Park Utah now has in use ten double-drum Turbinair hoists, and one Sullivan double-drum a. c. hoist of the same capacity and outside design as the air hoists. The electric hoist is slower than the air hoists and does not pass large boulders easily; it is, however, a very effective machine. The air hoists are fast, powerful and

Jan 1, 1925

By Allen J. Johnson

Anthracite coals have been divided into three groups: (I) meta-anthracite, a high-carbon coal that is usually very slow to kindle and difficult to burn, at least on conventional equipment; (2) anthracite, a high-carbon low-volatile coal of widely accepted value as both a domestic and industrial fuel; and (3) semianthracite, a coal lying between anthracite and bituminous coal in carbon and volatile content, and also, generally speaking, in burning characteristics. Anthracite Groupings The technical differentiation between these groups, as defined by the A.S.A.-A.S.T.M. Sectional Committee on the Classification of Coals, is as shown in Table I. Tables 2 and 3 show typical analyses of anthracites and semianthracites and Figs. I to 3 show graphically the range of analytical samples. Table 4 shows the commercial sizes of coals. Meta-anthracite and Graphitic Anthracite Typical analyses from virtually every field in the United States indicate that there are few if any extensive deposits of meta-anthracite. Some of the anthracites of Rhode Island contain almost negligible quantities of volatile and would thus fall into the meta-anthracite grouping on a basis of analyses alone. However, their other characteristics indicate that it is doubtful whether they should be considered as fuels at all, but rather as graphite. In fact, this material is being mined for use as foundry facings and furnace linings.4 A typical analysis of Fenners Lodge graphite,4 from Rhode Island, is: graphitic carbon, 55.9 per cent; silica (ash), 40.6; sulphur, 1.6; moisture, 1.9; volatile, o. Other Rhode Island coals possess percentages of volatile that would throw them into the normal anthracite rather than the meta-anthracite class. However, this "volatile" is nearly all noncombustible,3,4 being composed almost entirely of carbon dioxide and inert gases, therefore its definition as volatile is open to discussion, leaving the exact classification of the fuel a moot question. One factor is certain, Rhode Island coal is so different from nor-mal anthracite in both analysis and burning characteristics that it should have a

Jan 1, 1944

By Allen J. Johnson

Anthracite coals have been divided into three groups: (I) meta-anthracite, a high-carbon coal that is usually very slow to kindle and difficult to burn, at least on conventional equipment; (2) anthracite, a high-carbon low-volatile coal of widely accepted value as both a domestic and industrial fuel; and (3) semianthracite, a coal lying between anthracite and bituminous coal in carbon and volatile content, and also, generally speaking, in burning characteristics. Anthracite Groupings The technical differentiation between these groups, as defined by the A.S.A.-A.S.T.M. Sectional Committee on the Classification of Coals, is as shown in Table I. Tables 2 and 3 show typical analyses of anthracites and semianthracites and Figs. I to 3 show graphically the range of analytical samples. Table 4 shows the commercial sizes of coals. Meta-anthracite and Graphitic Anthracite Typical analyses from virtually every field in the United States indicate that there are few if any extensive deposits of meta-anthracite. Some of the anthracites of Rhode Island contain almost negligible quantities of volatile and would thus fall into the meta-anthracite grouping on a basis of analyses alone. However, their other characteristics indicate that it is doubtful whether they should be considered as fuels at all, but rather as graphite. In fact, this material is being mined for use as foundry facings and furnace linings.4 A typical analysis of Fenners Lodge graphite,4 from Rhode Island, is: graphitic carbon, 55.9 per cent; silica (ash), 40.6; sulphur, 1.6; moisture, 1.9; volatile, o. Other Rhode Island coals possess percentages of volatile that would throw them into the normal anthracite rather than the meta-anthracite class. However, this "volatile" is nearly all noncombustible,3,4 being composed almost entirely of carbon dioxide and inert gases, therefore its definition as volatile is open to discussion, leaving the exact classification of the fuel a moot question. One factor is certain, Rhode Island coal is so different from nor-mal anthracite in both analysis and burning characteristics that it should have a

Jan 1, 1944

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10&apos; to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.&apos; The damaging action of sulfur on the malleability of cobalt has not been generally recognized,&apos;; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By E. S. Grumell

THE correct sampling of coal and coke is becoming important to an ever increasing number of producers and consumers. This, therefore, may be an opportune moment to examine where we stand with regard to existing and proposed methods. In this paper an attempt will be made to review, as briefly as possible, some of the considerable amount of painstaking research which has been done in the last 10 years, and which has unquestionably led to a much better understanding of the subject. In so doing we shall try, on the one hand, to make clear where substantial progress has been made, and on the other hand, to draw attention to points that require further investigation. The paper is divided into sections in order to emphasize the major divisions of the subject; further, in order to retain this emphasis, detailed consideration of some of the points has been relegated to appendixes. No attempt has been made to give a complete survey of the literature, as this has already been done by L. A. Bushell.2 The following abbrevia-tions will be used: A.E., average error; P.E., probable error; S.W.R., size-weight ratio; B.S.I., British Standards Institution.

Jan 1, 1939

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.&apos; It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By Donald L. Katz

FIFTEEN years ago Dr. Manning published a paper in "Petroleum Development and Technology" on &apos;.Fundamental Research Relating to Petroleum." He tabulated for several industries "the proportion of their present success which can be fairly attributed to the application of information and processes obtained by scientific research," giving petroleum a score of 7 compared to 100 for the electrical and coal-tar industries. Today the petroleum industry as a whole and the producing groups both have raised their score beyond the majority and are climbing toward the top. Present practices are being developed both by fundamental research and the application of the research method in field operation.

Jan 1, 1941

By L. R. Smith

BUTANE OPERATED drilling rigs are a recent innovation in the petroleum industry, so extensive data on their operation are not available. However, experience indicates that, within limitations, as much can he accomplished with butane as with steam, at a decided reduction .in expense of installation and cost of operation. Commercial butane is a liquid motor fuel similar to gasoline, but much more volatile, so that it has to be stored under pressure. At 10° F. it is liquid at atmospheric pressure, but at 100° it has a pressure of 70 lb. or more. As soon as the pressure is reduced, it turns to vapor and in that state is far more easily mixed with the air necessary for combustion. Butane occurs as a by-product in the absorption process of natural gasoline extraction from casing-head gas. The product has been used to some extent 10 raise the octane value of gasoline. However, because of its volatile nature, such admixture is stable only to a limited degree. Attempts also have been made to introduce the product in a gaseous form into oil- hearing formations in repressuring work. It has, however, until recently, for the most part been wasted.

Jan 1, 1937

By Fredrick C. Kruger

Introduction This surprisingly little-known group of minerals, the nonmetallics, so-called for their lack of metallic luster, is the largest group of the mineral kingdom, and cinstitutes perhaps 75 percent of all mineral species. For the most part, these minerals are compounds of the common acids, oxides, hydroxides, and two elements, carbon and sulfur. The list of the non- metallic minerals, therefore, is very long. It includes the borates, carbonates, chlorides, fluorides, nitrates, phosphates, silicates, sulfates, and less commonly, arsenates, chromates, molybdates, suliides, tungstates, and vanadates, the latter groups, and many of the oxides, being sought principally for their metal content. Those nonmetallics used commercially are generally called the industrial minerals, although in addition this term also includes a considerable group of rocks. The list of industrial minerals and rocks is continually growing as new uses are found, and it now numbers over 300 commodities. The industrial minerals industry has developed since about 1920. There- fore, the development has been fast, and it has been more or less parallel with the development of the art of minerals beneficiation. General Discussion of the Group This group is so heterogeneous that it has defied logical, or widely accepted, classification, whether by origin, composition, or end use, and perhaps for this reason the industrial minerals generally have received short shrift in both teaching and research. Except for those involved with asbestos, cement, fertilizers, gypsum, salt, sand and gravel, few large companies have deigned to enter the field, and consequently most industrial minerals have been developed for the most part by the small operators or entrepreneurs. Yet surprisingly, except for one war year, the nonmetallics have always surpassed the metals in value and tonnage (Fig. 1). One main characteristic that most of the nonmetallics have in common is direct sensitivity to labor and transportation. In other words they are characterized by large bulk and low-unit value, and hence have what might be termed a "place value".

Jan 1, 1971

By John Birkinbine

The experience of the past five years has furnished opportunities to study and to partially explain the operation and some of the causes of the short blast of Warwick Furnace at Pottstown, Pennsylvania, as described in the paper read at the Lake Superior Meeting, in August, 1880.* The many inquiries concerning the details of furnace operation which followed the publication of the paper, and the expressed desire of furnace managers to be informed as to future operations of this plant, have encouraged the preparation of the following data. To make the record continuous, and add to the value of both contributions, the present paper commences where the review of a short blast of Warwick Furnace ended, and includes the data of another short blast of two months, and a subsequent continuous campaign of nearly five years, which, by comparison, we shall designate as "the long blast." Frequent visits to the plant in the five years, during which its operation could be studied, and correspondence with the manager, Mr. Edgar S. Cook, have given a knowledge as to general features and details, and the courtesy of the officers of the Company which has given free access to the books of record permits the presentation of data which it is believed will be welcomed by furnace managers. Interest will undoubtedly be increased by the remarkable results which Mr. Cook has achieved chiefly with anthracite coal in a furnace whose details of construction will scarcely be generally admitted as embodying advanced ideas, its height being but 55 feet, with a bosh diameter of 15 feet 6 inches, its bosh-slope comparatively flat, its crucible smaller than the average, and the heat of the blast never reaching 1000&apos; Fahrenheit. At present writing the credit of the best anthracite blast-furnace practice recorded in our Transactions is conceded to be that pursued by Mr. Fackenthal, at the Durham furnace, and Mr. Cook, at War-

Jan 1, 1886

By W. C. Hagel, H. J. Beattie

Phases present at 2200° and 1500°F (1204° and 816°C) were identified in sixty wrought developmental austenitic alloys possessing wide compositional variations. The bases were iron-, cobalt-, and nickel-rich as well as a base with equal parts of each. There are only two structure types previously not found in similar alloys, viz .-the Co3 W and the Fe3Al types. A molybdenum-rich monocarbide decorates dislocations with unusual clarity. Other results provide correlations between alloy composition and phas e precipitation. Grouping intermetal -lic phases into three general classes : I) geometrically close-packed, 2) topologically close-packed, and 3) bcc derivatives, the nickel base prefers the first, the iron base the second, and the cobalt base the third—each base tending to shun the other two classes. Thus, a crystal-chemistry effect previously noted by Laves and Wallbaum can he expanded for these Group VIII elemental bases. There appear to he no quaternary or higher -order structure types requiring more than three atomic species. AFTER studying aging reactions in many diverse commercial austenitic alloys1-4 as a function of detailed time-temperature variations in heat treatment, it became apparent that matrix composition influenced structure types and morphologies to a large extent. These tendencies were related4 to a crystal-chemistry effect uncovered by Laves and Wallbaum.5,6 We have now directed our efforts to exploration of the whole ternary field, covering the standard base elements—iron, cobalt. and nickel— with 10 to 20 pct Cr and moderate amounts, up to 10 pct, of the usual alloy additions. Solutioning and aging treatments were held constant with major emphasis on X-ray identification of microconstituents. The possible existence of exceptions to the Laves-Wallbaum effect, or any new phases, was sought. Phases appearing in austenitic alloys can be classified as geometrically close-packed (gcp), octahedral or nonoctahedral interstitial compounds, topologically close-packed (tcp), semicarbides, and bcc derivatives. Crystal structures of the first four classifications can be visualized as a dense packing of semirigid spheres of different sizes, while the bcc derivatives represent a less efficient packing of spheres. The Laves-Wallbaum effect involves the gcp and tcp phases. Gcp phases possess both tetrahedral and large octahedral interstices; examples are Ni3Ti(n), NiSAl(y&apos;), Co3W(E), and other ordered AB3 compounds where B atoms are smaller than A. Their precipitation is primarily intragranular, presumably coherent with an austenitic matrix, and a chief source of strengthening. Most octahedral interstitial compounds (e.g., CbC, Tic, TiN, Mo2C) have a gcp lattice of large metal atoms which accommodate small carbon or nitrogen atoms in the octahedral interstices. The compound Ti2SC, previously designated Y phase or T phase, can, with some reservation due to its partial co-valency, be placed in this category.7 The nonoctahedral interstitials (e.g., M7C3, Fe3C) represent close-packings of spheres in structures that provide larger triangular-prism interstices for carbon, since the octahedral interstices formed by chromium and iron atoms are too small. Tcp phases possess only tetrahedral interstices; examples are Laves (Fe2Ti, Fe2Cb, Fe2W...AB2), p(Fe7MO6, Co7W8.... A8B7), and (FeCr, Co2Cr3)

Jan 1, 1965