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By R. L. Robinson, P. DeFrank, R. F. Hatfield

Production equal to or greater than open-hole completions is possible through perforated completions if the flow paths throughout the perforations are free of obstructions.' Previous investigations have indicated that, in some cases, maximum productivity is not obtained due to plugging of the perforations with debris from the wellbore fluid and/or debris from the perforating process. Control of wellbore fluid and proper well completion techniques are very important in the elimination of perforation plugging.' Selection of properly designed perforating equipment also is quite important for maximum well productivity. Studies made with the use of the perforation flow laboratory, in which perforating tests are run under simulated well conditions, have shown that perforation plugging occasionally occurs. Plugs in perforations result from various causes. One of the contributors to plugging that can be controlled by the perforating device is the slug or carrot resulting from jet perforating. This condition has undergone extensive study, and previous developments have resulted in a decrease in carrot size—but not in complete elimination. It was felt that, if a method of completely eliminating the carrot could be found (with charge performance equal or better than previously obtained), a significant contribution would have been made. Such a charge has been developed and is reviewed in this paper. THEORETICAL CONSIDERATIONS OF CARROT ELIMINATION There are several popular theories of how a shaped charge jet is formed."," One of these is the hydrodynamic theory, wherein the liner is treated as a fluid under the impact of the explosive forces. Another is the spalling theory, where the interaction of shock waves in the liner causes small particles to be torn from the inner surface of the liner and projected at high velocity toward a common focal line to form the jet. It is not unreasonable to assume that both of these theories may be partially correct. For purposes of our discussion, it is simpler to use the second theory. Generally speaking, when a plate of metal is attacked by an explosive shock pulse, the pulse is transmitted through the metal at high velocity, as shown in Fig. 1(A). Pressures at the shock front may be 6 X 10' psi or higher. This shock wave (a compression wave) upon striking a free surface, Fig. 1(B), is partially reflected back as a tension wave. The interaction of the tension wave with the decaying compression wave causes a stress concentration in the metal; when this stress becomes great enough, a failure occurs and a small particle flies off and is projected away from the metal surface, as shown in Fig. 1(C). A new free surface is then presented to the shocks; the process repeats itself until there is no longer enough energy to cause failure, leaving a portion of the metal relativcly untouched. See Fig. 1(D). To apply this theory to a perforating shaped charge, consider the flat plate to be folded into a somewhat conical shape, with a column of explosive placed in intimate contact with the cone (Fig. 2). An explosive initiator detonates the charge, creating a shock wave

By E. T. Turkdogan

In this theoretical paper, a transport-reaction mechanism is suggested for the enhancement of the rate of vaporization of metals, or other materials, brought about by the process of convection and condensation. Based on theoretical reasoning it is predicted that, when there is a temperature gradient surrounding the heated object, a slight increase in the rate of vaporization brought about by natural convection is enhanced further as a result of condensation of the vapor close to the surface of the object. In order to derive the effective vapor-concentration profile, consideration is given to the super saturation of the vapor necessary for the homogeneous nucleation of the condensed phase from the vapor. For the formulation of the rate equation based on this mechanism, adequate information should be available on the transport properties of gases and vapors at elevated temperatures and the method of calculating nucleation pressures of the vapor. The methods of deriving such data are discussed in the paper and a rate equation is calculated for the vaporization of iron in helium for various temperature gradients in the boundary layer. Considerations are also given to the effect of oxygen on rates of vaporization of metals under isother ma1 and nonisotherma1 conditions. THE study of the methods of enhancement or retardation of basically transport-controlled vaporization reactions is of theoretical interest with possible practical implications. There are several ways of bringing about such effects. For example, Turk-dogan, Grieveson, and Darken1 demonstrated that the rates of vaporization of metals under isothermal conditions were increased by several orders of magnitude, up to the maximum rate attainable in vacuo, by introducing some reacting gas into the inert atmosphere surrounding the metal. Such an effect is brought about by the interaction of the counter-diffusing reacting gas and metal vapor in close proximity of the metal-gas interface. Another case which is often experienced in practice is that of vaporization affected by natural convection. Although several theoretical and experimental studies of this problem have already been made, no detailed consideration has been given to the possible effects of condensation of the vapor in the boundary layer on vaporization rates, which constitutes the subject matter of this paper. BASIC CONCEPT OF ENHANCED DIFFUSION-LIMITED VAPORIZATION When a heated object, for example a metal sphere, is submerged in a fluid medium, heat is transferred from the surface of the object to its surroundings by four simultaneously occurring transfer processes: i) free-molecular conduction at the gas-solid interface over the distance equal to the mean free path of the gas, ii) conduction and convection through the fluid-dynamic boundary layer, iii) latent heat of mass transferred, and it!) radiation. The free-molecular conduction becomes pronounced only when the total pressure in the system is very low, e.g., below 1 mm Hg. Therefore, this term may be neglected for ordinary pressures. At low mass-transfer rates, due to vaporization of the object, the contribution of process iii) to the heat transfer can also be neglected. Finally, since the temperature profile is not affected by radiation, the latter need not be considered. The natural convection is brought about by gravitational body forces arising from a decrease in the

Jan 1, 1964

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith' indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.'' Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By E. T. Turkdogan, P. Grieveson

Molten silver is equilibrated with silicon nitride at 1400°C in nitrogen + hydrogen gas mixtures, and from the solubility data the activity coefficient of silicon is found to be 1.76 at silicon concentrations below 1 pct. Using this value, and that available from the silicon cmbide solubility measurements, together with those derived from the phase equilibrium diagvam, the activities of silver and silicon are estimated for the entire composition range. The main feature of the activity data is that there is a pronounced positive deviation from ideality. The activity of silver in molten silver containing up to 5 pct Si was determined by Schadel, Derge, and Birchenall1 by measuring the vapor pressure of pure silver and of the alloy over a temperature range of 850º to 1050°C. They deduced from their results that there is a positive deviation from Raoult's law and that the activity coefficient of silver increases with decreasing temperature. However, as pointed out by Kubaschewski and Catterall,2 their activity coefficients are much too high, giving silver activities greater than unity. At a later date McCabe and Birchenal13 showed that the previous vapor pressure data on silver4 were high by a factor of about 1.3; presumably a similar error must have occurred with the vapor pressure measurements on the Ag-Si alloys. The activities of silicon and silver calculated by tager' from the phase diagram and by Gibbs-Duhem integration, respectively, show a positive deviation from Raoult's law for silicon activity and positive and negative deviations for the silver activity. According to these computations, at infinite dilution of silicon ygi = 1.12 at 1420°C. d'Entremont and chipman6 measured the solubility of silicon carbide in molten silver at unit carbon activity; the equilibrium silicon content is found to be Nsi = 0.017 ± 0.002 atom fraction for 1420°C. Using the data of Grieveson and Alcock7 for the free energy of formation of silicon carbide from pure silicon and graphite, the activity of silicon for unit activity of carbon and of silicon carbide is asi = 0.0308 at 1420°c; therefore for the above solubility data on silver, YSi = 1.81, which is somewhat higher than that given by Hager. Use is often made of silver alloys in the measurements of activities of solutes in metals where silver has a very low solubility; in fact, Ag-Si and Ag-A1 alloys have been used in the past for such purposes. In an attempt to gain more thermodynamic data on molten Ag-Si alloys, measurements have been made in the present study on the solubility of silicon nitride in molten silver; the results on these solubilities are given in this paper together with a detailed discussion of activities of silver and silicon. SOLUBILITY OF SILICON NITRIDE The standard free energy of formation of silicon nitride is known with a reasonably high degree of accuracy. According to the measurements made by Hincke and Brantle8 and by Pehlke and Elliott,' the following are the free energy data for the standard states of solid Si3N4, liquid silicon, and Nz at 1 atm pressure:

Jan 1, 1963

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By J. E. Johnson

(Cleveland Meeting, October, 11,1912.) THE subject of blast-furnace slag is one which has had much consideration, particularly from the scientific standpoint, and several years ago technical literature contained many learned discussions on the oxygen-ratio of the acids and the bases, all on the assumption that acids and bases must be present in a ratio depending on molecular weight and chemical valency. Much work has also been done, sometimes in conjunction with the former, on the total heat and the temperature of initial fusion or softening of various slags. A wider knowledge of the blast-furnace now enables us to say that for practical purposes this work has been of almost no value. It is now generally admitted that on the physical side the important point of a given slag is neither its total heat of fusion nor its softening-point, but its free-running temperature, since this is the critical temperature of the furnace. This temperature bears no definite relation to the softening-temperature, as determined by Seger cones, for instance, because some slags melt relatively like ice, with a very short viscous-range, while others melt relatively like tar, with a very long viscous-range. In one the difference between the softening- and the free-running temperature may be very small, as little as 100° F., while in another this difference may easily be 200° or 300°. The importance of this difference is so great in practice as to destroy completely the value of exhaustive investigations, even such as those of 0. Boudouard, published a few years ago.1 * Presented also at the Joint Meeting of the Institute with Section IIIa, Metallurgy and Mining, of the Eighth International Congress of Applied Chemistry, New York, September, 1912. 1 It may not be amiss at this point to call attention to the excellent suggestion of Woolsey McA. Johnson, made several years ago, for determining the temperature at which different slags have the same practical fusibility. This suggestion

Oct 1, 1912

By Frank W. Dickson, George Tunell

Five hot spring areas of the western United States show evidences of present day deposition of HgS; two also show evidences of accompanying Sb2S3 deposition. Sulfide minerals are depositing at or near the surface from hot waters that differ for each spring ai:ea in amount and kinds of dissolved matter. All the springs contain dissolved substances that act as buffering agents and that cause increased alkalinity with increasing temperature. Transport of Sb2S3 is possible in H2O and in boron and sulfide solutions. Increasing alkalinity and temperature enhance stibnite solubility. Quantitatively important transport of HgS appears restricted to alkaline sulfide solutions that contain HgS2=. Elemental mercury probably forms in deep hot waters because HgS breaks down into mercury and sulfur above 200°C, and free S is removed by reaction with water. Elemental mercury should accompany HgS2= in solutions that were at 200°C or higher. Cinnabar deposits from saturated alkaline sulfide solutions because of combinations of temperature decrease, dilution, oxidation, and reactions with wall rock: Amedee Hot Springs, Boiling Springs, and Coso Hot Springs are areas in which HgS is the only sulfide deposited. Hot waters at Amedee and Boiling Springs are supersaturated with HgS or transport colloidal HgS. Steamboat Springs waters deposit mainly silica and stibnite, but they have deposited HgS recently. Sulphur Bank waters deposit mostly stibnite and some HgS. The hot-spring waters of all springs represent highly modified deep water. Field and laboratory studies support the concept of transport of HgS in moderately alkaline sulfide solutions as HgS2=. Fluctuating deposition of stibnite and cinnabar reflects availability of sulfide or variations in deep-source HgS and Sb,S,. Silica and HgS dissolve mutually in alkaline sulfide solutions, and cinnabar and quartz would be expected to deposit simultaneously. Free mercury given off by hot-spring waters would impregnate country rocks.

Jan 1, 1968

By R. G. Baughman

With the constantly increasing sales competition, coal to be sold today must meet the test of quality in every respect. The producers must be able to make all marketable sizes that will meet such general requirements as follows: 1. Ash content must be consistently low, depending upon the use to be made of the coal. 2. Sulfur content must be controlled accurately according to requirements. 3. All sizes must be positively free from visible impurities. 4. Free moisture of washed sizes must be reduced to a minimum. 5. The freezing of wet coal in cars must be prevented. 6. The percentage of fines in small mixed sizes must be controlled to give the uniform and proper combustion when used on various types of automatic stokers. 7. The undersize particles or degradation caused by handling must be kept to an absolute minimum in all sizes loaded. Many difficulties may be met in bringing any particular coal to meet these quality requirements, because the extent to which the quality of a coal may be controlled is determined largely by its physical characteristics. Preparation of an Impure Coal Bed The application of modern and scientific methods in the controlled preparation of bituminous coal from a bed in the mid-western field will illustrate the results that can be accomplished by adequate preparation: The bed referred to contains coal inherently excellent as to low ash and other desirable characteristics; in fact, the coal itself is one of the best in the field. It is, however, divided into four layers by dirt bands of soft shale 1 to 2 in. thick. It also contains much sulfur in the form of sulfur lenses and laminated sheets. Horsebacks or rolls varying from 6 in. to 12 ft. in width are encountered in the mining of the bed and heretofore have rendered it practically unworkable. The mines operating in this

Jan 1, 1931

For the past several years the policy of a large section of our mining industry in relation to our present bureaucratic form of government has become increasingly amusing, if not a little disgusting. In the past, mining men have always featured themselves the self-announced champions of free enterprise, and, generally, this conviction, was substantiated by their deeds. In recent years, however, a large group of the industry, while still expounding, from the front porch, the principles of free enterprise and a sound economy based upon the law of supply and demand, have gone around to the back door with palm extended, to join labor, farmers, bureaucrats, and other pressure groups to get their share of the take. The procurement of subsidies, bonuses, increased metal prices, and government assistance in a multitude of forms seems to have obscured from their thinking the welfare of the country as a whole and the sounder economic principles of a balanced budget and lower taxes. At the recent Colorado Mining Association convention in Denver, I. was alarmed to see just how far this specialinterest type of thinking has progressed within the mining industry. Government assistance to mining. was generally considered inadequate, and a flat bonus for any new mineral discovery was proposed. It was disquieting, too, to learn how far the federal alphabet agencies have entered into the mining industry and of the thousands of highly paid technical. men on the federal payroll required to man these numerous overlapping agencies and bureaus. Now all this is very fine, and some aspects of the federal give-away program can be very appealing to the unsuspecting in the mining industry as they have been to those in other groups. Some of these expensive programs may bring about a few dividends or even several new mines. But to this whole line of pump-priming reasoning there is one big disastrous fallacy.

Jan 1, 1952

By S. M. Marshall, A. C. Richardson, H. Y. Yancey

A year ago, Marshall and Bird presented a paper in which a new method of measuring the agglutinating power of coal was described.' The procedure used was to determine the strength of a button containing 10 parts sand and one part coal, formed by carbonizing the mixture in a crucible in an electric furnace. The result of the determination was reported as the total weight in grams required to bring about complete destruction of the button. Correlations were shown between the agglutinating value and some of the characteristics of the different coals that were investigated. This agglutinating test has been in use fairly continuously during the past five years for coals of widely differing coking qualities, and it has shown reasonably concordant results accurate enough for commercial use, although there are many features of the test which should have further scientific study. During the past year a study has been made of some coals of low coking strengths, and incidental to the main investigation some data which appear to be of interest and value were obtained on the loss in agglutinating power caused by exposure to the air. Three coals were investigated, all of which were of the Tertiary age; two were from one field in Asia, and one from a field in the United States. The three were similar, as shown by the proximate and ultimate analyses in Table 1 (moisture-free basis). Coals SA and RA generally contain about 5 per cent. moisture and coal P about 3.5 per cent. moisture on the as-received basis. The large difference in the ash contents of the coals, amounting to practically 10 per cent. between SA and RA, and P, makes difficult a direct comparison of their qualities. In the second section of Table 1 the figures have been put upon an ash-free basis., This table shows that these coals are closely alike. The ultimate analyses are almost identical except for the higher nitrogen content of

Jan 1, 1930

R. MOLDENKE, Watchung, N. J. (written discussion*).-It is some-what difficult to discuss the paper of Mr. Stork, when the description of the cupola melting occurrences indicates that his practice is open to question. The evident burning of much of the steel charged,. coupled with the remarkably low silicon content of the mixture as shown by the resulting product, throws the entire melting practice into that of making cupola malleable. If anything is wanted here, it is a. high bed to melt upon, and yet Mr. Stork in the very beginning of his paper speaks of the evils of oxidation due to a "high" bed, etc. The experienced foundry-mall would judge at the outset that Mr. Stork has kept his bed in the cupola too low, and naturally got a lot of oxidation from the blast. The oxidation of steel when used in large quantities in cupola mixtures is a well-known phenomenon, and is readily understood. One has but to. put a file into the forge fire and watch it burn when heated high enough. The melting point of steel being higher than cast iron, heavy pieces may dig way into the bed before being completely melted away, the last por-tions being directly exposed to free oxygen from the blast. Another situation not to be forgotten is the oxidizing effect of carbon dioxide at high temperatures. A serious oxidation of the steel is quite conceivable if in the zone of maximum carbon dioxide and minimum carbon monoxide-free oxygen being entirely absent. Hence the well understood practice of never melting a mixture with much steel unless the bed is kept exceed-ingly high; or again the above-mentioned malleable practice. Mr. Stork mentions the impossibility of deoxidizing a heat. after the steel contained has been oxidized. This is true to a great extent with the ordinary deoxidizers, such as silicon and manganese, but can be brought about by vanadium, titanium, magnesium, etc. Proper melting, however, makes this unnecessary.

Jan 10, 1919

V. H. GOTTSCHALK, Rolla, Mo. (written discussion*).-In connection with Mr. Waring's quotation of Urbain's work, attention may be drawn to a remark found in the report of the session of the Société de Chimie Physique,1 held in December, 1909, that, while all blendes contain gallium in larger or smaller quantities, those blendes carrying indium are generally free from germanium, and vice versa. Urbain, furthermore, . expresses his conviction that this behavior, being related to the condi-tions of deposition of the ore, should be an important factor in determining the origin and mode of formation of zinc blende deposits., In. searching the literature for the naturally expected sequel to these remarks, there is found a report on the extraction of germanium from blende, after many months' work, on a commercial scale;2 then a paper3 on some Spanish blendes, all containing cadmium, examined by Urbain's 'method (this paper contains, also, very important work on the com-position and color of blendes, as well as on the occurrence of organic .matter and of inclusions in such blendes), and a second paper on Spanish blendes in general, in which this original point of Urbain's concerning the relative quantities of the three rare elements is taken up.4 Angel del Campo finds that of 68 specimens examined, four only were entirely free of germanium, gallium, and indium;. 38 had small proportions, while 19 were notably, and seven relatively rich in the three rare metals. He found the relative frequency to be: gallium in 60, germanium in, 50, and indium in 38; all three occurred in 29 cases; germanium and gallium together in 18; gallium and indium together in four; germanium and indium together without gallium, in none; four had gallium only, three had germanium only, and one had indium only; in 23 it appeared feasible to extract these elements. Finally, it may be worth mentioning that the discovery of gallium in commercial aluminum5 brought forth two

Jan 1, 1918

By W. T. Thom

Many able men have contributed to the subject of coal classification, and recent publications on the subject have indicated a crystallization of opinion in that connection which promises the development in the near future of a scheme of coal classification which will be of real and increasing value to coal producers and users, as well as to those interested in coal on more exclusively scientific grounds. It is obvious that such a classification must be simple; must be based upon readily ascertainable factors; and if properly developed will apply to the whole range of coals between peat and anthracite and not merely to certain types of coal. Many of the numerous schemes of classification proposed in the past have given quite satisfactory results when applied to the higher rank coals, but have broken down when applied to the younger coals of higher moisture, and, as previously pointed out by the writer,' this breakdown has been due to the practice of ruling out "moisture" as an essential component of the volatile matter reported in the customary proximate analysis of coal, whereas a review of the mode of formation and natural history of coal satisfies us that moisture is a normal and natural ingredient among its volatile constituents; and a knowledge of analytical practice shows that the "moisture" and "volatile matter" reported are both mixtures of moisture and volatile matter, rather than sharply differentiated distillation fractions. After an extended consideration of the subject the writer regards the conventional proximate analyses of coals as affording the information essential for a both practically and scientifically satisfactory c1assification—assuming that the coal samples compared have been collected and analyzed according to standard methods. Two variables are required for a workable classification, and these appear to be afforded by the calorific value and proportion of volatile constituents (including moisture) credited to the coal on an ash-free basis. The writer originally proposed that the figures used for classification purposes be those given for the "air-dried" and "ash-free" form of the proximate analysis,

Jan 1, 1930

By H. W. Paxton, G. M. Pound

A method is outlined for taking into account variation in chemical potential of both components in evaluating capillary effects at growing interfaces. The results are compared with experiment, and seem to be in reasonably good accord for Widman-statten ferrite growing in austenite. ENERY pointed out that during the steady-state growth of phases with a rather small radius of curvature at their advancing edge capillarity cannot be neglected. By proper application of the Laplace equation a correction must be made to the activity gradients down which diffusion occurs. Subsequent workers have concerned themselves with attempts to evaluate specific cases by the use and modification of the principles laid down by Zener.2-5 To solve the problem in its simplest form it is necessary to assume thermodynamic equilibrium at the interface and to select some criterion which will allocate the available free energy between reversible and irreversible processes. Zener chose to assume that the division should be made such that the new phase grew at the maximum rate. Other workers have used the same2,3 or different assumptions, e.g., maximum rate of free-energy dissipation,4 minimum rate of entropy production.5 Li6 has proposed that the "thermokinetic potential" should be a minimum at steady state. The purpose of this presentation is to note that most prior treatments have considered variations due to capillarity only in the chemical potential of the mobile constituent, and that a more consistent treatment must involve a consideration of the variation of chemical potentials of both solute -and sol- vent in a binary system.* As an example, the way in which this arises for ferrite growing from austenite may be illustrated by reference to Fig. l(a). The line OABC shows a typical variation of carbon activity with composition at one atmosphere pressure (at a transformation temperature below A3). In the tip of a growing ferrite plate with a hemi-cylindricab leading edge of radius ?, the pressure due to capillarity is*

Jan 1, 1963

By H. C. Kenny

The annealing or softening temperature of cold-worked copper is appreciably increased by almost unbelievably small amounts of silver. As indicated by some data in this paper, the softening temperature of high-conductivity, tough-pitch copper may be increased from 200" to 350" C. by the addition of only 15 oz. per ton (0.052 per cent) of that element. Because it has this higher annealing temperature as compared with the silver-free metal, silver-bearing copper finds considerable use in industry. For example, when hard-rolled copper is used in operations that involve soldering or tinning, silver-bearing copper insures against loss of strength, whereas silver-free copper becomes "dead soft." Yet—though several investigators, beginning with Caesar and Gernerl in 1916, have shown that small amounts of silver do definitely raise the softening temperature of copper—data are lacking on the problem: What is the specific influence of different amounts of silver on this temperature? It was to help in filling this gap in the knowledge of what might be termed "alloy coppers" that the data given herein were obtained. The softening of cold-worked copper depends, of course, on a number of factors, of which the composition of the material is only one. Other highly important factors are the degree to which the material is cold-worked and the time it is held at the annealing temperature. The method of cold working and the grain size of the metal produced are also significant. All these variables were taken into account in the investigation reported here, and the influence of silver on the electrical conductivity and on the working was also considered. The coppers used in the softening tests were Lake coppers melted and cast by the Calumet and Hecla Consolidated Copper Co. The ires were fabricated by the Roebling Wire Co. and the sheets were rolled at the Battelle Memorial Institute. Partial analyses of some of the coppers are listed in Table 1, with their electrical conductivities.

Jan 1, 1934

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.' In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

By M. E. Nicholson

The solubility of carbon in Ni-Cu alloys was determined at 1000°C. The factors which limit solid solubility are discussed with particular reference to the influence of electronic factors. The results indicate the extent of solid solubility is a function of the density of states at the Fermi surface. THE solid solubility of an interstitial element is primarily limited according to Seybolt and Fullman1 and Speiser and Spretnak2 by (a) the strain energy produced when the solute atom takes its interstitial position, and (b) the partial molal free energies of the solid solution and the coexisting phases. In several binary systems of a transition and a noble metal, where there are no abrupt changes in strain energy or free energies of coexisting phases, the solid solubility of an interstitial third element drops abruptly to a negligible value at a composition corresponding to a complete filling of the "d-band." Such a decrease occurs in the case of hydrogen in the Pd-Ag system at 60 pct Ag.3,4 The solubility of carbon in Ni-Cu alloys seems to vary in a similar manner as indicated by the embrittling effect of carbon on these alloys. These al- loys are embrittled by slow cooling due to the precipitation of graphite. This embrittlement can be removed by heat treatment if the carbon content is less than the solid solubility limit at the heat-treating temperature. If the carbon content of the alloy exceeds the solid solubility at the heat-treating given temperxture, the embrittlement cannot be eliminated by solution heat treatment.' Since pure nickel has a carbon solubility of 0.25 wt pct6 at 1000°C, embrittlement is easily removed from commercial nickel and nickel-rich alloys, which may contain of the order of 0.10 wt pct C. Embrittlement due to carbon cannot be removed from Ni-Cu alloys containing 70 to 80 wt pct Cu by annealing unless: the carbon content is of the order of 0.04 wt pct CL or less."' Thus, it appears that the

Jan 1, 1962

By B. Amadei

INTRODUCTION Laboratory studies on the deformability and strength of intact rocks generally involve the uniaxial compression test, the standard triaxial compression test and direct or indirect tension tests. If [al ,a2 ,a3] are principal stresses [(al>a2>a3)] with compression taken as positive and tension taken as negative, the applied stress field for each one of these tests can be represented as shown in Fig. 1. However, for most in-situ conditions, such as those that exist at any point around an underground excavation, the stress field is truly three-dimensional or multiaxial [(al+ a2+a3)] and none of the tests shown in Fig. 1 can be used to predict the mechanical behavior of the rock. There are special cases for which one of the three principal stresses vanishes. Biaxial loading of rocks in-situ takes place, for instance, when rocks deform and fail in plane stress conditions. This can occur in a free unloaded surface of a rock structure such as in the wall of an underground excavation or a rock slope. Parallel to the free surface, the stress field components can be both compressive [(al>a2>0)], both tensile [(O>a2>a3)], or mixed, one component being compressive and the other one tensile [(U~>O>U~)]. The purpose of this paper is to present the results of 25 true biaxial tests that have been conducted on cubical specimens of Indiana Limestone using the multiaxial cell available at the University of Colorado at Boulder. The tests include uniaxial compression and tension, biaxial compression and combined biaxil compression- tension. Flexible fluid cushions and brush bearing platens were used for compressive and tensile loading respectively in order to minimize loading end effects on the test specimens. The paper begins with a review of previous investigations on the multiaxial behavior of rock. Then, test results are presented in terms of

Jan 1, 1984

By W. A. Selvig

BY plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Com-mittee on Coal Classification. This scheme was sponsored by Sub-committee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic.. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as follows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group, 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. , The lignitic class of coal was divided into two groups both below 8,000.B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934

By W. H. Ode, W. A. Selvig

By plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Committee on Coal Classification. This scheme was sponsored by Subcommittee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as fo1lows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. The lignitic class of coal was divided into two groups both below 8,000 B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934