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By Ernst A. Hauser

IN a paper published three years ago,' the term "silicic chemistry" was used for the first time to emphasize the increasing importance of the chemistry of silicon in science and technology. The development through which the colloid chemistry of siliceous matter has gone since then is in itself ample proof that the coining of this new term for this branch of colloid science was not presumptuous. Until quite recently, however, silicic chemistry concerned itself only with the composition and colloidal properties of natural and synthetic siliceous matter, but had not paid much attention to the genesis of this matter, particularly to that of the clay minerals. What is even more disturbing, particularly from an educational point of view, is the fact that neither mineralogy, geology, nor metallurgy has fully realized the important role colloidal phenomena must have played in the genesis of our planet and the formation of minerals generally speaking. Considering the importance of colloid chemistry today in the fields just mentioned, it is not surprising that the theories most agreed upon by geologists and mineralogists for the origin of clay minerals are not acceptable from a strictly colloid chemical point of view for the genesis of these most important and most abundant components of the earth. Of all the theories pertaining to the origin of clay minerals, those still most accepted by geologists and mineralogists are the "residual clay" and the "transported clay" theories.15 The former is based primarily on the assumption that the formation of clay minerals is the result of surface weathering of fresh rocks, or is due to the action of solutions. Taking the action of water on orthoclase as an example, the most recent ideas have been summarized by H. Jenny13 as follows:

Jan 1, 1952

By A. L. Marshall, F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C.oin a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. APPARATUS AND TECHNIQUE The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 0800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard' glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not 'a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by

Jan 1, 1944

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

[Separates of all the Technical Publications published in 1930 are available at Institute headquarters. All the papers are on file in public, university and technical libraries, and when so indicated in the list, may be found in the Transactions.] Metal Mining Technical Publi- Title Author Meeting Tran~. cation Volume No. and Page* 264-A.29 Quicksilver Industry in 1929. Im- L. H. Duschak San Francisco T30, 283, 319 provements in the Metallurgy of C. G. Maier and Oct., 1929 Quicksilver and Symposium on The others Present Status of the Quicksilver Industry (With Discussion) (37) 271-A.30 Observation on Ground Movement R. E. Palmer New York T30. 168 and Subsidences at Rio. Tinto Feb.. 1930 Mines, Spain (20) 274-A.31 Development and Installation of the C.L.Berrien New York T30, 139, 166 Hawkesworth Detachable Bit (29) Feb., 1930 276-A.32 Protective Measures . Against Gas 0. A. Glaeser New York T30, 129. 167 Hazards at United Verde Mine (11) Feb., 1930 287-A.33 Use and Cost of Compressed Air (12) R. S. Lewis New York Feb., 1930 314-A.34 Miami Copper Company Method of F. W. Maclcnnan New York T30, 39, YO Mining Low-grade Orebody (44) Feb., 1930 319-A.35 How Human Beings Respond to W. J. McConnell New York Changing Atmospheric Conditions Feb., 1930 (9) 324-A.36 Vertical and Incline Shaft Sinking at Arthur B. Foote San Francisco T30, 87 North Star Mine (21) Oct., 1929 32bA.37 Governmental Control of the Pro- W. E. Colby New York duction and Sale of Mineral Re- Feb.. 1930 sources (With Discussion) (16) 333-A.38 Some Recent Developments in Open- E. E. Hunner New York T30, 106, 117 pit Mining on the Mesabi Range Feb.. 1930 (25) 334-A.39 Mining Methods and Costs at Presi- V. D. Howbert El Paso dio Mine of American Metal Co. of R. Bosustow Oct., 1930 Texas (15) 339-A.40 Operation of Pressure Fans in Series W. 8. Weeks New York (8) V. 6. Grishkevich Feb., 1931 364-A.41 Top Slicing with Filling of Slices as H. Willey El Paso Used at the Charcas Unit of Com- Oct., 1930 pania Minera Asarco, S. A. (17) 373-A.42 Drill Sampling and Interpretation of H. T. Matson New York Sampling Results in the Copper G. A. Wallis Feb.. 1931 Fields of Northern Rhodesia (17)

Jan 1, 1930

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..' and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young's modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen's5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

DISCUSSION, G. Derge and D. J. Girardi presiding N. A. Gokcen (Michigan College of Mining and Technology, Houghton, Mich.)—While the authors present very interesting results on the effect of sulphur upon the solubility of oxygen, they have not established convincingly the lines of two-fold saturation (the valleys in Fig. 2) and the ternary eutectic point. Their contention that sample S-7, upon melting at

Jan 1, 1954

By J. P. Nielsen, H. Margolin, E. Ence

The Ti-Ni phase diagram has been investigated up to 68 pct Ni with iodide titanium base alloys by metallographic, X-ray, and melting point methods, and from 68 to 90 pct Ni by examination of as-cast structures of sponge titanium base alloys. NVESTIGATION of the nickel-rich portion of the I Ti-Ni phase diagram was first reported by Vogel and Wallbaum in 1938.' This work was subsequently extended to lower nickel contents by Wallbaum' who indicated the possibility of a eutectic reaction for nickel contents below 38 pct. Long et al.3 studied the titanium-rich portion of the phase diagram and found eutectic and eutectoid reactions below 38 pct Ni. However, the temperature of the eutectic indicated by Long et al. was considerably lower than that suggested by Wallbaum. Long and his coworkers synthesized their alloys by powder metallurgical techniques and encountered oxygen and/or nitrogen contamination. Thus the diagram which was obtained did not represent binary alloying conditions. However from these results the features of the binary diagram were predicted. At Battelle Memorial Institute4 the Ti-Ni diagram was investigated up to approximately 11.5 pct Ni with sponge titanium alloys. The range of temperatures used was not sufficient to define the eutectoid temperature or composition. The data of Wallbaum2 and Long et al.8 were of particular interest for the present study, and although the work was originally concerned with the region below 40 pct Ni, the investigation was extended to higher nickel contents in an attempt to resolve the differences between these workers. Experimental Procedure Preliminary work on the Ti-Ni system was carried out with duPont Process A sponge titanium alloys to reduce the amount of subsequent work to be done with iodide titanium base alloys. The sponge titanium used contained 99.71 to 99.77 pct Ti, 0.1 pct Fe and 0.005 to 0.009 pct Ni. The iodide titanium obtained from the New Jersey Zinc Co. contained 99.9 to 99.95 pct Ti. Nickel used with sponge titanium was 98.9 pct pure. The high-purity nickel alloyed with iodide titanium was cobalt-free with approximately 0.05 pct C and was obtained through the courtesy of the International Nickel Co. The 15 g sponge titanium charges for melting were prepared by compacting in a die or by placing the weighed portions of nickel and titanium directly into the furnace. Iodide titanium charges were made by drilling holes in the as-received rod and inserting the nickel or by wrapping the nickel in sheet. Sponge titanium alloys containing from 0.2 to 90 pct Ni and iodide titanium alloys containing 0.2 to 68 pct Ni were prepared by these methods. In addition to these alloys several 1/2 1b sponge titanium alloys were supplied by the Allegheny Ludlum Co. The charges were melted in an arc furnace under an argon atmosphere. The procedures used were similar to those reported in the literature5,' and the furnace has been described.' Except for iodide titanium alloys with 40 to 68 pct Ni (see section on copper contamination), each alloy was melted for 1 min, then either turned over or broken before re-melting for an additional minute. Currents of 200 to 400 amp were used depending on the melting point of the alloy. Prior to heat treatment, alloys containing less than 14.5 pct Ni were hot-forged at 750°C. With the exception of alloys in the homogeneity range of the compound TiNi, alloys of higher nickel contents could not be hot-forged. Heat treatment of iodide titanium base alloys was carried out in argon-filled quartz capsules which were broken under water at the conclusion of heat treatment to quench the specimens. Temperatures were controlled to ±5oC and annealing times up to 48 hr were used. For melting point determination, specimens were placed in carbon crucibles which were in turn en-capsuled in argon-filled quartz capsules. The start of melting was determined by rounding of corners and by metallographic examination. Complete melting was considered to have occurred at that temperature at which the specimen assumed the shape of the crucible. Specimens were prepared for metallographic examination by mechanical polishing or by an electrolytic procedure." For alloys containing up to 80 pct Ni Remington A etch7 50 pct glycerine, 25 pct HNO,, 25 8 HF) was used. For higher nickel alloys aqua regia and Carapella's etch (5 g FeCl,, 2 ml HNO,, and 99 ml methyl alcohol) were employed. Specimens to be exposed for powder patterns were prepared by filing, by breaking specimens in a

Jan 1, 1954

By AIME AIME

AT Williams College, in the quaint old New England town where people still go to the post office for their mail, an interesting institution has come into being as one of the aftermaths of the peace conference at Paris in 1919. The war taught the world many things about economics although much remains to be learned and more to be appreciated. B. M. Baruch, H. A. Garfield, president of Williams, and others who took part in the conference at Paris or in preparation for it, feeling that benefits would accrue from informal friendly discussion of the problems that lead to political differences between peoples, called together a summer conference in 1920. This has now become an annual affair and is coming to be looked upon as an important center for developing and stimulating public opinion. Membership in the Institute is by invitation and the lists change to correspond with the particular subjects taken up. Each year a number of distinguished foreign public men are invited to be the guests of the Institute and to meet men and women from various parts of the United States interested in their special subjects. Round tables, general conferences, and public lectures are the means employed to bring out discussion. The first are organized by groups, each including usually 25 to 40 people interested in a special subject and meeting three times a week for informal discussion. Teachers, writers, economists, engineers, business men, indeed men of all vocations and many shades of opinion, are brought together. Once a week each round table presents in general conference with the members of all other groups the more general conclusions reached in its own decisions. Afternoon and evening lectures are given by the foreign guests and these are open to the public. The lectures and the general conferences are reported widely in the press but the proceedings as a whole are not printed, no resolutions are passed, and no action is taken or contemplated. The whole plan is to furnish a forum for free discussion in hopes that the difficulties of various groups and peoples may be taken up sympathetically and good understanding promoted. There is no creed, doctrine or dogma to which the Institute is committed and widely different views are currently presented. The constant effort is to bring out points of view and the reasons for them rather than to build up convincing arguments favourable to a specific action

Jan 1, 1926

By AIME AIME

NEW place was assigned to the women for their headquarters at the annual meeting of the Auxiliary but they, as usual, occupied a large place in the activities of the annual meeting. The alcove on the Thirty-ninth Street side of the building was a busy place on Monday morning, as the members of the various sections from New York to California greeted each other. The registration was conducted under the supervision of Mrs. Wolfes, Miss Georgene Davis and Mrs. Jennings, while Mrs. Hursh, Mrs. Hyde, Mrs. Charlton Reynders, and others dispensed tickets to the various functions that had been provided for entertainment. There seemed to be the usual number registered, but when only one member of the District of Columbia Section made herself known everyone wondered why the large delegation of last year had so dwindled. The explanation appeared next day, when a number of others from that Section arrived, telling of a delightful reception on the night before, at the White House. Mrs. Hoover had honored the "Canaries"¬(the organization of Lone Girl Scout' workers) the officers of the Section, and their husbands, who for once became only "so and so's husband." Luncheon was served on the fifth floor on Monday, the hostesses for that day being Mesdames C. F. Ayer, Willis Burns, G. W. Farny, H. G. Moulton, and T. T. Read. A number of sight-seeing trips had been arranged for the afternoon. The most popular proved to be an expedition to the new Riverside Church; where Dr. Fosdick is pastor. Guides were there to conduct

Jan 1, 1931

By Lyall Zickrick

NUMEROUS brands of virgin pig lead are used in the manufacture of lead and lead-alloy cable sheath for commercial cables. In changing from one brand of pig lead to another a readjustment of press operating conditions is nearly always necessary. This is due largely to different flow characteristics, and some brands extrude at a much lower pressure than others; for example, copper-bearing lead requires much more pressure than a low-bismuth lead under the same operating conditions. With the modern type of lead press the extrusion practice in general differs very little. Molten lead at a temperature of 375° to 400° C. (710° to 750° F.) is cast in a water-cooled cylinder and allowed to cool or solidify into a slug for six to nine minutes. . This slug is forced into the die block and around the core tube through which the cable runs. The die block is held at an optimum temperature by means of gas flames, usually 175° to 225° C. (350° to 4.35° F.). Measurements of the tem¬perature of the cable sheath taken at the time of extrusion have covered a range of 190° to 225° C. (375° to 435° F.). According to Tammann, the rate of extrusion for a metal under constant pressure through a simple orifice is almost doubled for each 10° C. rise in temperature. Because of the irregularity of die-block construction, such a great increase is not obtained in lead-cable extrusion practice. To obtain more" definite information about the effect of small per¬centages of metals usually present as impurities in virgin pig lead, a series of compression tests were made covering several different brands of lead and various alloys. Since the usual temperature of the sheath is approxi¬mately 200.° C. as it emerges from the die block, these compression tests were all performed at 200° C. Five different brands of virgin pig lead were selected, as follows: Brand A: A desilverized western lead of very high purity. This lead contains neither copper nor bismuth. Brand B: A bismuth-free southeastern Missouri lead, usually con¬taining 0.05 to 0.08 per cent copper. Brand C: A copper-free mid-western desilverized lead of very good grade, usually containing around 0.06 to 0.10 per cent bismuth.

Jan 1, 1932

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By Lyall Zickrick

Numerous brands of virgin pig lead are used in the manufacture of lead and lead-alloy cable sheath for commercial cables. In changing from one brand of pig lead to another a readjustment of press operating conditions is nearly always necessary. This is due largely to different flow characteristics, and some brands extrude at a much lower pressure than others; for example, copper-bearing lead requires much more pressure than a low-bismuth lead under the same operating conditions. With the modern type of lead press the extrusion practice in general differs very little. Molten lead at a temperature of 375" to 400" C. (710" to 750" F.) is cast in a water-cooled cylinder and allowed to cool or solidify into a slug for six to nine minutes, This slug is forced into the die block and around the core tube through which the cable runs. The • die block is held at an optimum temperature by means of gas flames, usually 175" to 225" C. (350" to 435" F.). Measurements of the temperature of the cable sheath taken at the time of extrusion have covered a range of 190" to 225" C. (375" to 435" F.). According to Tammann, the rate of extrusion for a metal under constant pressure through a simple orifice is almost doubled for each 10" C. rise in temperature. Because of the irregularity of die-block construction, such a great increase is not obtained in lead-cable extrusion practice. To obtain more definite information about the effect of small percentages of metals usually present as impurities in virgin pig lead, a series of compression tests were made covering several different brands of lead and various alloys. Since the usual temperature of the sheath is approximately 200" C. as it emerges from the die block, these compression tests were all performed at 200" C. Five different brands of virgin pig lead were selected, as follows: Brand A: A desilverized western lead of very high purity. This lead contains neit,her copper nor bismuth. Brand B: A bismuth-free southeastern Missouri lead, usually containing 0.05 to 0.08 per cent copper. Brand C: A copper-free mid-western desilverized lead of very good grade, usually containing around 0.06 to 0.10 per cent bismuth.

Jan 1, 1932

By A. L. Sweetser

Experience has shown how difficult it is to obtain information regarding laboratory-tests in connection with the chlorina-tion-process for the extraction of gold from its ores, and I therefore present the following method, somewhat in detail, for the benefit of those who may desire to pursue research work in this field. The ore chosen was a partly-decomposed porphyry, extremely siliceous and comparatively soft, and of an average value per ton of from $25 to $26 in gold and $0.68 in silver. The chemical analysis gave: Fe,O,, 3.35; FeS, 1.5; MnO,, 0.75; ZuCO,, 4; A1,0,, 3.20; H,O, 0.7 ; SiO, and insol., 83.50 per cent. The ore, first crushed to pass a 5-mesh screen, was coned and quartered until a 45-lb. sample was obtained. Samples for assay and analysis, taken from this lot by means of riffles, were crushed to pass a 100-mesh screen. The original sample was divided into 10-lb. lots, of which one was crushed to pass a 10-mesh screen; another through a 12-; the third through a 20-, and the last through a 30-mesh screen. Because of the production of an excessive quantity of fine material it was deemed inexpedient to crush finer than 30-mesh size—a decision the wisdom of which is proved by the data in Table I., showing the increasing ratio of slimes, in proportion as the ore is crushed finer. In order to determine the percentage of fines in the sizes of mesh selected, a weighed sample of ore was taken from each mesh, and a sample from the 10-mesh lot was passed successively through 20-, 40- and 100-mesh screens, and the percentage remaining on each screen determined. This process was repeated with the 12-, 20- and 30-mesh lots, with the results given in Table I.

Jan 1, 1908

By Oliver Bowles

WAR necessities have spurred inventive genius in many fields. A grinding mill without any moving grinding parts stirs the imagination. Among the new and striking accomplishments in the heterogeneous group of nonmetallic industrial minerals is the use of an electric arc to speed up manyfold the difficult and delicate task of drilling a microscopic hole in a diamond, the hardest of all known substances. Outstanding in the field of optical research is the ability that man has developed to improve upon nature by making in the laboratory optical crystals many times larger than those usually found in rocky crevices. These are merely samples of numerous events and circumstances of noteworthy import, many of which are recorded in this review. Termination of the second World War in 1945 permits an appraisal of the effects of the conflict and the probable effects of the coming restoration of a peacetime economy on the nonmetallic mineral industries. Some industries were stimulated greatly by the war, notably mica, quartz crystal, graphite, spinning asbestos, potash, fluorspar, barite, and refractories. The large-tonnage industries connected with the building trades, however, were forced to curtail their activities, except where their products were needed for wartime construction. Their reconversion to peacetime production will not be difficult.

Jan 1, 1946

ALABAMA Anniston.-Carrington, F. G. Auburn.-Brown, R. L. Battelle.-Green, G. G. Bessemer.-Abbott, C. E. Dobbs, G. G. Ferguson, V. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Bonnyman, J. Bowron, J. Bush, M. W. Crawford, G. G. Crockard, F. H. Ellis, E. E. Fairbairn, C. T. Gallacher, J. Geismer, H. S.

Jan 1, 1917

By Donald L. Colwell

THIS is a metallurgical war. More than ever before, the mechanized forces and the air-borne warfare are deciding campaigns. Both of these are primarily dependent upon metals. There are two ways of increasing the effective supply of these metals when the demand is greater than the total over-all supply. The American custom, when a shortage of anything develops, is to get more. In the case of some nonferrous metals this has been done. For example, our potential peak output of magnesium will be almost one hundred times the prewar production. Output of aluminun has also been tremendously increased, and production of other metals is being stimulated by every possible means. Our enemies, however, have another successful method of increasing the effective supply of a material, and that is, to eliminate entirely all nonessential uses, and also to use, in essential applications, alternate materials wherever possible. Sometimes, ersatz material is inferior to the original, and consequently does not do the job as well. Often, however, it has been found superior, and many substitute items are now being used both by industry and by the military which will continue even when the original material again becomes available.

Jan 1, 1943

By C. Crussard, R. Tamhankar

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers accord-ing to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Gerhurd Derge Carnegie Institute of Technology Schenley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Staff Coordinator, James J. Burke THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chiprnan, Vice President; T. D. Jones, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. W. Thornton, Chairman; Dennis Carney, John Chip-man, J. C. Fulton, J. H. Hollomon, H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: T. B. King, Chairman; S. J. Dickenson, R. P. Hermsdorf, R. Schuhmann, Jr., and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman, F. Lincoln Vogel, Jr., Vice-chairman, W. A. Backofen, R. W. Balluffi, J. H. Bechtold, M. B. Bever, R. S. Busk, C. G. Goetzel, Paul Gordon, C. D. Graham, .Jr., Robert F. Hehemonn, R. I. Jaffee, F. E. Jaumot, Jr., Irving R. Kramer, A. J. Lena, Harold Margolin, C. J. McHorgue, Russell A. Meussner, J. B. Newkirk, H. W. Paxton, G. E. Pellissier, I. S. Servi, Alan U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B. King, F. C. Langenberg, W. 0. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 29 West 39th Street, New York 18, N. Y. Telephone: PEnnsylvania 6-9220. Subscription $20 per year for non-AIME members in United States and North, South, and Central America; $25, foreign; $5 for AIME members. Single copies, $4.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed in its publications . . . Copyright 1958 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AIME New York ... Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts... Second class postage paid at New Yark, N. Y., and Ann Arbor, Mich. Volume 212, Number 6.

Jan 1, 1959