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What has happened to the basic coal industry during the past year? Has it been a better year for coal than 1961? What striking new developments have occurred in mining, preparation and utilization? Are there positive signs that production will go up? What has happened in the utility market, the metallurgical market and the export market? Is the controversial question of coal transportation nearer to a solution? What progress has research made for coal during the year? The answer to these and many other important questions are offered in the following review of the Coal Industry-1962.

Jan 2, 1963

By F. B. WEEKS

I HAVE chosen for my subject a mining district which in an article published four years ago I referred to in the following words: "One of the un- usual anomalies of mining development and history is that a district having added thirty or more millions of wealth to a principal mining state, situated within four to six miles of two transcontinental railways and two auto highways, and within 150 miles of the most widely advertised part of the United States, should have been so completely lost sight of that probably not one mining man in ten can tell offhand where it is situated." But this district never was a dead one: it was only slumbering. During the past four months, day by day, it has been emerging from that state of slumber.

Jan 1, 1929

By Charles Will Wright

FRANCE will be given a large portion of the Marshall Plan funds for relief, reconstruction, and industrial development in France and in her colonial possessions. At present that country is not in position to export any large tonnages of the mineral products needed in the United States. However, if, through Marshall Plan aid and private capital investment, production of these products can be largely increased, agreement should be made by which the United States is to get a substantial portion of such increased output in part payment for the material and technical aid they receive. France issued a decree, published in the "Official Gazette" on Feb. 3, 1948, which permits conversion into dollars of dividends derived from dollar investment in Government-approved projects and will agree to a scale of capital amortization to be determined in each individual case. This decree is to encourage private capital to cooperate with local capital in industrial undertakings. The French Colonial Ministry has prepared an extensive program for aid to the mining industries in overseas possessions to be undertaken by

Jan 1, 1948

By L. D. Jaffe

IN 1945-1946, the author measured temper brittle-ness in ingots of varying composition prepared by remelting SAE 3135 bar stock under vacuum. Since other investigators1-" have been referring to this hitherto unpublished work, belated publication seems worthwhile. Steel in 7 lb batches&apos; was induction melted with nickel additions in a magnesia crucible under a pressure of 10 microns of Hg or less and cast into a 2 in. diam chill mold. The compositions of ingots A, B, and C prepared in this way are shown in Table I; the vacuum melting lowered carbon, manganese, sulphur, and nitrogen content. Ingot B was homogenized 24 hr at 1095°C; ingots A and C were not homogenized. Blanks, M in. square, were cut from each ingot, austenitized 1 hr at 870°C, water quenched, tempered 1 hr at 595"C, and water quenched. Half the blanks from each ingot were given an embrittling treatment of 50 hr at 455°C and water quenched. A few specimens, embrittled and unembrittled, were finally heated 1 hr at 580°C and water quenched. Charpy specimens machined from the blanks were V-notched on the side closest to ingot mid-radius and paired as to radial position in the ingot, one of each pair having received the embrittling treatment and the other not. Specimens were broken in a standard impact machine at various temperatures, the same temperature, in general, being used for both bars of a pair. Fig. 1 shows the results. It is evident that temper brittleness, as measured by the increase in temperature of transition from brittle to tough failure introduced by the 455°C treatment, was decreased but not eliminated by reducing carbon to 0.006 pct, manganese to < 0.004 pct, and nitrogen to 0.001 pct. In another study," temper brittleness was apparently eliminated by -reducing carbon to 0.003 pct, with 0.80 pct Mn and 0.0015 pct N (ingot D)." • Analyses given for carbon below 0.02 pct were made by Jensen method; for nitrogen, by Kjehldahl method. Values quoted else-where&apos;-&apos;." for carbon content of ingot C and for nitrogen content of ingot D were obtained by conventional combustlon and by vacuum fusion methods, respectively, and are considered much less accurate. The 580°C final treatment removed previous em-brittlement (ingot B particularly), indicating that this was "reversible embrittlement."" Metallographic examination of ingot C with 1 pct nital etch revealed only ferrite; ingot A had carbide spheroids uniformly distributed in a ferrite matrix. With ethereal picric acid plus zephiran chloride etchant.&apos; no differences between embrittled and un- embrittled specimens of ingots A, B, or C were noted. Fracture of C and D below the transition temperature was predominantly transcrystalline, with traces of intercrystalline, in both embrittled and unembrittled conditions. The corresponding fracture of unembrittled B was mixed transcrystalline and intercrystalline; of embrittled B, predominantly intercrystalline with some transcrystalline areas. . . . Acknowledgment The efforts of J. C. Leschen, formerly of National Research CO~P., in preparing the ingots are acknowledged with thanks.

Jan 1, 1956

YEAR OF ELECTION 1922. FEDERICO GIOLITTI Torino, Italy. 1917. HERBERT HOOVER Washington, D. C. 1941. DANIEL COWAN JACKLING San Francisco, Calif. 1939. HENRY KRUMB New York, N. Y. 1942. Essington Lewis Melbourne Vic., Australia 1921. C. McDERMID London, England. 1942. PAUL DYER MERICA New York, N. Y. 1913. EZEQUIEL ORDONEZ Mexico City, Mexico. 1938. A.M. PORTEVIN Paris France 1937. JOHN V.W. REYNDERS, New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T.A. RICKARD Victoria, B.C., Canada

Jan 1, 1943

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) The following members registered at Institute headquarters during the month of April: J. C. Ralston, Spokane, Wash. E. P. Ross, Johnson City, Tenn. C. H. James, London, Eng. F. L. Garrison, Philadelphia, Pa. E. H. Benjamin, Oakland, Cal. A. Radcliffe, Copiapo, Chile. W. H. Shockley, Palo Alto, Cal. S. S. Wyer, Columbus, Ohio. A. C. Mauney, Salisbury, N. C. W. B. Kunhardt, Reading, Pa. A. W. Newberry, Los Angeles, Cal. W. E. Saunders, Philadelphia, Pa.

Jan 5, 1913

Jan 1, 1908

By N. A. Ziegler

THE chief difficulty in determining oxygen in steels is its tendency to form a variety of compounds. Almost every element, found as an ingredient in steels, maybe expected to be present as an oxide. Some of these oxides have widely differing properties, and consequently behave differently when attempts are made to reduce them by the vacuum fusion method. As I pointed out in a paper published in the Transactions of the A.S.S.T., Vol. 20, No. 1, many experimenters are spending considerable time and effort in attempting to deter¬mine the degree of completeness of the above reactions, and hold different opinions on the matter. In studying this subject the following table, taken from Hodgman and Lange&apos;s "Handbook of Chemistry and Physics" may be used as a guide.

Jan 1, 1933

During 1918, the activities of the United Engineering Society, the Library, the Engineering Foundation, and Engineering Council Were deeply affected by the war and much important war work Was done in our building. The endowment of Engineering Foundation was increased to $300,000 by an additional gift of $100,000 from Ambrose Swasey. By bequest of Dr. James Douglas, the American Institute of Mining Engineers received an endowment of $100,000, the income of which Will be expended in the maintenance of its library (now a part of the joint library). The Library Service Bureau has gained steadily; its business for 1918 amounted to nearly $10,000. Indexing of current engineering literature has been undertaken in conjunction With the Founder Societies and the Index is being printed in their publications. This service has been extended to the Engineering Institute of Canada and the Canadian Mining Institute. The expense is borne by the Societies. In this connection the American Society of Mechanical Engineers has purchased the Engineering Index heretofore published by "Industrial Management." In June the Westinghouse and General&apos; Electric Co. donated to the United Engineering Society their Patent Con¬trol Library of about 8000 volumes. Other noteworthy gifts Were a collection of 370 pieces relating to patent litigations, from Jesse M. Smith, and Dr. William Paul Gerhard&apos;s collection on gas engineering, transferred by the American Gas Association.

Jan 1, 1923

By Frederick A. Mumpton

For more than 200 years zeolites have been familiar minerals to geologists and mining engineers as minor, but ubiquitous constituents in vugs and fractures of most basalt and traprock formations. More than 35 different species have been recognized including several, such as chabazite, erionite, mordenite, and faujasite, whose adsorption properties rival those of many synthetic molecular sieves. Igneous occurrences of this type have never been mined on a commercial scale; they are generally small and low grade, and they commonly contain as many as four zeolite minerals, along with small quantities of calcite, quartz, and other silicate minerals. Their economic beneficiation to monomineralic zeolite products has also not been achieved and, for the most part, industrial applications of zeolites have relied primarily on synthetic molecular sieves that were crystallized from hydrous aluminosilicate gels. During the middle 1950s, when Union Carbide Corp. and other groups were developing processes and markets for their fledgling synthetic zeolite businesses, natural zeolites

Jan 1, 1975

By B. Kopelman, C. C. Gregg

THE reduction of tungstic oxide to tungsten metal powder by hydrogen is a process by which one might expect the resultant metal powder to he porous. In- deed, sponge iron, prepared by rcduction of the oxide in a reducing gas, is generally accepted as quite porous. with pores large enough to be seen readily under the optical microscope at relatively low magnifications. However, any pores that may exist in tungsten metal powder are not resolved by the optical microscope, and apparently, not even by the electron microscope. Fig r shows commercial tungsten powder magni- fied at I0,000 X by the electron microscope,&apos; both etched and unetched. In an earlier paper by one of the authors,* the existence of ports in tungsten powder was required to explain adequately the particle size changes occurring during the reduction of tungstic oxide. The inability to detect these pores under the electron microscope at 10,000 X implies that these {pores} are of a size of 100 A units or less. (This in itself is by no means proof that pores above 100 A would not exist, since polishing effects on the specimen might smear up holes of such small magnitude). If, then, these pores are less than IOO A. and of the order of molecular size, then the density of the metal powder should be

Jan 1, 1949

By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic&apos; displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. &apos;To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard&apos;s Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By E. W. Dewing

The solubility of A14C3 in cryolite melts has been determined by holding the melt with aluminum in a graphite crucible for 4 hr at temperature, quenching the crucible in water, and analyzing the frozen salt by CH4 evolution. The solubility is given by log(wt % Al4C3) = 1.298 -1.l74 (wt ratio NaF/AlF3) independent of temperature in the range 985" to 1080°C. Additions ofA1203, .NaCl, CaF2, or LiF up to 10 wt pct do not affect the solubility, provided that LiF and CaF2 are replaced by equivalent NaFin calculating the ratio. The variation with ratio can be accounted for quantitatively on the hypothesis that the Mechanism of solution is Al4C3 + 2AIF3 = 3Al2CF2 since the solubility varies as (aAIF3) 2/3; Mechanisms involving C", C2- , AlC- , A12C2+, and Al2CF+are re-jected. At ratios above 1.5 truces of c;- are also present. It was noticed some years ago in this laboratory that carbon specimens made cathodic in a cryolite bath decrease in diameter over a period of time.&apos; It was also found that cryolite which had been melted with aluminum in a graphite crucible was sometimes yellow, and that A14C3 could be seen intimately embedded in the cryolite crystals. CH, could be recovered by acid attack. There was thus reason to believe that A14C3 had a genuine solubility in molten cryolite, and the object of this work was to measure it. EXPERIMENTAL AND RESULTS A graphite crucible, 2 in. ID and 2.5 in. deep with a close-fitting lid, contained about 150 g of cryolite (plus additives) and about 20 g of 99.99 pct pure Al. It was placed in a vertical Inconel furnace tube, covered with refractory brick to provide thermal insulation, and the top of the tube was roughly sealed with disks of asbestos paper. An alumina tube led argon down to the level of the top of the crucible to expel air, and an alumina sheath with a Pt-10 pct Rh ther-mocouple inside was positioned between the crucible and the wall of the Inconel tube. The tube was heated in an electrical resistance furnace for the desired length of time; the refractory bricks were then removed, and the crucible was lifted out with tongs and quenched in water. After such a crucible was broken open it could be seen that its inner surface was yellow owing to the presence of A1,C3, and sometimes needle-like crystals could be observed (at X75 magnification) growing out into the nielt. It was concluded that Al,C, had been present as a separate phase when the crucible was at tenlperature and that the melt had been saturated: in

Jan 1, 1970

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a&apos;. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex &apos; and not completely understood. It has been proposed that hardening occurs in some alloys&apos; on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a&apos; marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium&apos; and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors&apos; reply)— -Williams&apos; arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams&apos; model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams&apos; model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams&apos; strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams&apos; model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By Charles A. Lindberg

Mobile cranes on tires are perhaps the most important accessory in truck-haulage pits. They usually are of 20-ton capacity at short radius and with outriggers but have considerable overload capacity. Standard booms are 30 ft but have 10-ft extensions with which they are usually operated. Cranes have two engines, both originally gasoline, but 150-hp Diesel engines have been found more reliable for the propulsion motor, the 100-hp gasoline motors being retained for hoisting. Pro- visions are made for dropping the ballast counter- weight to reduce axle weights to legal limits for highway travel. The weights are carried on a regular truck or are transported on an extra trailer axle behind the crane. Tractors-Probably equalling the cranes in usefulness are the track-laying tractors which are used to prepare roads and other surfaces, to clean up at the shovel, and for dozing on stripping dumps. A new type of tractor mounted on rubber tires has been tried out on the Mesabi Range for the past year and a half. The advantage of this design is its mobility which makes it capable of taking care of the spill at the shovel and then running to the dump to clean up. Alternating between these two jobs, it relieves heavy tractors that can be used to better advantage on heavier work that does not require so much traveling. This tractor can travel at speeds of 12 to 13 mph and is designed to facilitate repair of the expendable parts. Weaknesses have developed in the internal construction which have seriously marred the performance record of this unit, but when used within its capacity it is quite successful.

Jan 1, 1949

By J. P. Hirth, G. M. Pound

The flux of evaporation J from {loo) , {111), and (110) planes of silver single crystals and from poly crystalline specimens was measured at 744°C under a high vacuum using a time average weight loss method. The evaporation coefficient a was computed from the measured flux and vapor pressure data through the relationship J = aPe/21rmkT. The evaporation coefficients for the close packed planes and the poly crystalline specimens were found to be about 0.4 providing tentative confirmation of the theoretical limiting law for evaporation of metal crystals, a = 73(P/Pe) + % . The (110) planes faceted to form (111) planes, resulting in a greater evaporating area and larger a . The evaporation morphology of the plane surfaces and the surfaces of spherical single crystals is described in some detail. RECENTLY a detailed theoretical analysis of the mechanism and kinetics of metal crystal evaporation was made.1&apos;2 A mechanism for vaporization involving the recession of monatomic ledges across a metal surface was deduced, and evaporation rate equations were derived by considering the dynamics of these ledges. In most metals, the process of evaporation is one of dissociation of atoms from ledges, surface diffusion, and desorption. The gross vaporization rate is controlled by the surface diffusion and desorption rates. It was shown that the monatomic ledges, under the action of surface diffusion gradients, tend to assume a terminal velocity and spacing. Further, it was shown that crystal edges and grain boundaries are a ready source for monatomic ledges. In the case of evaporation of large, perfect crystals with clean, low-index surfaces, the kinetic treatment1 leads to a limiting law for crystal evaporation: where J is the gross flux of vaporization, a is the evaporation coefficient, Pe the equilibrium vapor pressure, m the atomic mass, k Boltzmann&apos;s constant, T the absolute temperature, and P the actual pressure of vapor over the crystal surface. Imperfections such as grain boundaries, pores, cracks, and macroscopic steps should have the effect of causing positive departures from this limiting law. Such an imperfection is a source for monatomic ledges, which, near their origin, are closely spaced and thus give rise to higher evaporation rates there. However, under many experimental conditions,&apos; this effect should be negligible due to the relatively low concentration of imperfections. In general, a more important cause of positive departure should be screw dislocations, and the effect of these has been considered in some detai1.2,3 Monatomic ledges emanate from points where the surface is intersected by a dislocation with a screw component normal to the surface. The dynamics of ledges arising from a screw dislocation are similar to those of ledges arising from a crystal edge. There is a perturbed region near the origin where the monatomic ledges are, under certain experimental conditions, closely spaced and the

Jan 1, 1960

By C. E. Sims

THE carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example,, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath. The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner without reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature. For the carbon-oxygen reaction C + 0 [=] CO this is expressed simply as [ ] where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1947

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