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By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.',' Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By G. P. Connell, R. E. Gilmore, J. H. H. Nicolls

The purpose of this paper is to suggest a procedure for indicating the dividing line between noncaking coals and those that have weakly caking properties. A laboratory agglomerating test as an aid in classifying weakly caking coals is outlined and its merits in comparison with the standard agglutinating method advanced by the U. S. Bureau of Mines are discussed. No attempt, however, is made to discuss in detail either the different methods for determining "caking" and "agglutinating" indices or the various systems of classification. Two methods, differing somewhat in procedure, have been employed and recognized as suitable for determining the caking or agglutinating values of coals; namely, those in which an inert material such as sand, electrode carbon, etc., has been mixed with the coal before being heated, and those in which the coal is carbonized alone. In all such methods, the coal with or without the inert material is in the finely divided state and the index or value sought is derived from the examination of the residue after heating in a closed crucible or other container. The procedure outlined by Selvig, Beattie and Clellandl is the most recent representative of the method using sand as inert material, while the agglomerating test described below is representative of the method in which the coal is carbonized alone. The standard volatile-matter determination affords a means for observing the coking properties of a coal, and this has been described by Rose2 as the simplest of all coking tests. According to him, "the resulting coke button will indicate whether the coal is noncoking, feebly coking or strongly coking," despite the fact that "almost every condition in this test is at variance with large-scale carbonizing practice." Lessing,3 the

Jan 1, 1934

By Robert Wamsley, W. E. Jones

ONE of the earliest problems in the life of any community is the provision of an adequate supply of water sufficiently free from all types of contamination to be suitable for domestic purposes. Generally speaking, the location of most communities is determined to a great extent by the availability of an adequate supply of satisfactory water. For a mining camp, that consideration cannot be foremost. Here, the ore takes first place, and the men who mine it must do the best they can under the existing conditions. If there is no local source of water, it must be brought from some distant source or must be found by sinking shafts or drilling wells. Fortunate indeed is the mining company that discovers a commercially valuable ore deposit beside a never failing creek full of pure water, with sufficient water rights available, because the acquisition of water in any other manner nearly always involves not only a considerable period of time but the expenditure of considerable money. The experience of Climax Molybdenum Co. demonstrates the measures that sometimes are necessary in order to provide a suitable supply of water. The Climax mine and mill are on the Continental Divide, about 13 miles northeast of Leadville. The elevation of the domestic part of the camp varies from a minimum of 11,320 ft. to a maximum of approximately 11,550 ft. above sea level, and, as is common at such altitudes, the near-by streams that might be suitable for a water supply are small and intermittent, usually flowing only during the summer months. The only streams of any size in the immediate vicinity of Climax are the Ten Mile and Arkansas Rivers. The headwaters of Ten Mile River are on the Company's property, and its water has been used for the domestic supply. The headwaters of the Arkansas River are about 2 miles distant and have not been used as a source of supply by the company. During the past 11 years of the production of molybdenum at-Climax, the number of families living there has increased from about 45 to 283, and the population has increased from about 200 to 1200 persons. Consequently, the capacity of the water-treatment facilities, and the amount of water available, had to be increased to meet the requirements of the camp. As early as 1932 it was recognized that the water in Ten Mile River would not continue to be adequate for domestic purposes and after considerable discussion it was decided to drive a drift through the major fault in an effort to find additional water. This drift was completed in 1935 and tapped sufficient water to make the supply adequate. This water was treated in a tank underground, where lime was added, and was then piped into the domestic supply lines. At about the time this line was completed, the presence of fluorine in harmful concentrations was discovered in the water. This problem was submitted to the International Filter Co. and in November 1937 a plant of its design was put in operation for treating the water to remove the fluorine. This plant proved entirely successful,

Jan 1, 1945

?AARONSON, ALFRED E , Vice-Pres , Mid-Co Petroleum Co, Mid-Co Bldg, Tulsa, Okla '18 ABADIE, EMILE R, Min Engr Address wanted '76 || ABADILLA, QUIRICO A, Geol Dept, Cia Mexicana de Petroleo "El Aguila," S A, Edifico "El Aguila," Esq, Calles Aurora y Comercio, Tampico, Tamaulipas, Mexico '20 ABBOTT, CLARENCE E, Gen'l Supt, Iron Mines Div, Tenn Coal, Iron & R R Co, 1405 Minnesota Ave, Bessemer, Ala '04 ABBOTT, LOUIS BENJAMIN, Chief Engr, Consolidation Coal Co, Elkhorn Div, Jenkins, Ky '15 ABBOTT, ROBERT R Met Engr, Peerless Motor Car Co, Cleveland, Ohio '12 ABE, ASAKA Fujita Min Co, Dojima, Osaka, Japan '14 ABEEL, GEORGE H, JR, Cons Min Engr, 635 St Paul Ave, Los Angeles, Cal '18 ABEL, ALBERT E, Asst to Pres, Valley Mould & Iron Corpn, Sharpsville, Pea '19 ABEL, W D, Min Engr Forum Bldg, Sacramento, Cal '19 ABELL, O J, Pres & Treas, Abell-Howe Co, 332 South Michigan Ave, Chicago, Ill '19 ABERNATHY G E Willow Springs, Mo '20

Jan 1, 1923

By Benjamin C. Craft

Oil and gas development in Louisiana during 1935 brought this state at the close of the year up to fourth place in the nation as a producing area. A review of development in North Louisiana centers around Rodessa, the most important reserve discovered in this area in many years. While the producing limits have not been defined, this discovery is one of the major developments of the year. New gas fields were discovered in Lincoln, De Soto and Bossier parishes. The Lincoln Parish discovery, completed flowing a highly saturated gas from the Glen Rose, further indicates the importance of deep-seated prospects in the interior salt-dome area. Minor extensions were made at Sligo and Pine Island. During the year, 126 oil wells and 103 gas wells were completed in North Louisiana as compared with 144 oil wells and 68 gas wells during 1934. The North Louisiana oil production was 9,617,405 bbl. as com-pared with 9,274,050 bbl. during 1934, an increase of 343,355 bbl., while the gas production increased 18 billion cu. ft. in 1935 over its 1934 figure. The Louisiana Department of Conservation gage of Nov. 1, 1935, shows an open-flow capacity of 4,563,725,000 cu. ft. per day from 941 wells in the Monroe field and 682,770,000 cu. ft. from 159 wells in the Rich-land field. A great deal of leasing continues in North Louisiana as a result of the Lincoln Parish discovery and development in the Rodessa field, especially in Bossier, De Soto, Winn, Lincoln, Bienville, Webster, Ouachita and Richland parishes. South Louisiana's position as an area of important reserves was further proved during the past year. Increased drilling resulted in the discovery of seven new fields: Lafitte, Garden Island Bay, Tepetate, Bunkie, St. Martinsville, Jeanerette and Big Lake. New sands or producing horizons proved productive in 15 of the proven fields. The total oil production for South Louisiana during 1935 was 40,731,-056 bbl. as compared with 23,255,437 bbl. during 1934. There were 222 oil and gas wells completed in South Louisiana during 1935 as compared with 214 oil wells during the previous period. Drilling during

Jan 1, 1936

By Benjamin C. Craft

Oil and gas development in Louisiana during 1935 brought this state at the close of the year up to fourth place in the nation as a producing area. A review of development in North Louisiana centers around Rodessa, the most important reserve discovered in this area in many years. While the producing limits have not been defined, this discovery is one of the major developments of the year. New gas fields were discovered in Lincoln, De Soto and Bossier parishes. The Lincoln Parish discovery, completed flowing a highly saturated gas from the Glen Rose, further indicates the importance of deep-seated prospects in the interior salt-dome area. Minor extensions were made at Sligo and Pine Island. During the year, 126 oil wells and 103 gas wells were completed in North Louisiana as compared with 144 oil wells and 68 gas wells during 1934. The North Louisiana oil production was 9,617,405 bbl. as com-pared with 9,274,050 bbl. during 1934, an increase of 343,355 bbl., while the gas production increased 18 billion cu. ft. in 1935 over its 1934 figure. The Louisiana Department of Conservation gage of Nov. 1, 1935, shows an open-flow capacity of 4,563,725,000 cu. ft. per day from 941 wells in the Monroe field and 682,770,000 cu. ft. from 159 wells in the Rich-land field. A great deal of leasing continues in North Louisiana as a result of the Lincoln Parish discovery and development in the Rodessa field, especially in Bossier, De Soto, Winn, Lincoln, Bienville, Webster, Ouachita and Richland parishes. South Louisiana's position as an area of important reserves was further proved during the past year. Increased drilling resulted in the discovery of seven new fields: Lafitte, Garden Island Bay, Tepetate, Bunkie, St. Martinsville, Jeanerette and Big Lake. New sands or producing horizons proved productive in 15 of the proven fields. The total oil production for South Louisiana during 1935 was 40,731,-056 bbl. as compared with 23,255,437 bbl. during 1934. There were 222 oil and gas wells completed in South Louisiana during 1935 as compared with 214 oil wells during the previous period. Drilling during

Jan 1, 1936

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators1,2,3 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By John Chipman, Carl F. Floe

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By Carl F. Floe, John Chipman

A year ago the authors published a paper on the solubility of sulphur dioxide in molten copper.l The data in that paper agreed closely with that obtained by previous investigators, which, however, did not agree with the theoretical predictions for solubility of triatomic gases of this type. It has generally been assumed that the reaction of solution is: 6Cu(l) + SO2(g) = Cu2S (in Cu) + 2 Cu2O (in Cu) [I] _ (CU2S)(CU2O)2 K = (Cu)6(Pso2) [2] Neglecting the slight change in copper concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume of gas absorbed, it follows that this volume should be proportional to the cube root of the pressure. It was found that a plot of the volume absorbed versus the cube root of the pressure gave a straight line, but that this line did not pass through the origin. Calculations of the equilibrium constant for the reaction showed that it was fairly constant for pressures above 100 mm. but that actually it approached zero at lower pressures. The conclusion was made therefore that the solubility as determined could not be expressed by Eq. I or by any other simple equation, particularly at low pressures. Other investigators have concluded that the solubility of sulphur dioxide in copper as well as in several copper alloys is more nearly proportional to the square root of the pressure.* Such a conclusion, however, does not satisfactorily account for the results, even when rather complicated mechanisms for the solution are assumed. The highly improbable speculations of Lepp2 and of Schneider and Esch3 based upon hypothetical dissociation pressures of Cu2O and CU2S dissolved in copper illustrate the type of reasoning that has been used to account for the discrepancy. In the discussion of the previous paper, the authors pointed out that the discrepancy might possibly be due to impurities in the copper, although the purest form available was used. Further consideration of the problem suggested that the impurities likely to have the greatest effect on the solubility of so2 in copper were oxygen, sulphur and carbon. Accordingly, further experiments have been made to show the effects of these elements. Experimental Methods The apparatus used for measuring solubility was essentially the same as that shown in the previous paper. However, since it was desired to make measurements at low pressures, a McLeod gauge was added and 6-mm. glass tubing was substituted for the capillary. This increased the "hot volume" considerably but was necessary in order to obtain good vacuums in a reasonable length of time. A mercury diffusion pump was also installed.

Jan 1, 1942

By S. R. du Toit, W. J. Oberholzer, M. I. Watson, D. G. Krige

The objectives, essential features and implications of the 'random' and 'deterministic' types of ore value surfaces are examined as well as the basic requirements for a satisfactory prediction model. The 'random' method used on the South African gold mines and based on observed auto-covariance patterns is briefly discussed as well as its justification in preference to the 'deterministic' approach. Various mathematical models for auto-covariance patterns are examined for the one-dimensional case. It is also shown that these patterns as estimated for ore values in certain mines agree closely for various sizes of ore unit. In two case studies the variations in gold, uranium and ore thickness covariance patterns are examined and compared with certain geological features established independently from sedimentological studies.

Jan 1, 1969

By N. M. Langdon

Spokane Meeting, September, 1909.) THE following corrections to the paper of Mr. Langdon (Bulletin No. 34, October, 1909, pp. 919 to 940), received after the publication of the paper in the Bulletin, will be incorporated in the paper as finally published in the forthcoming Vol. XL. of the Transactions, but are here presented for the information of members:' Page. 921. Table I., furnace M2, item 11. For " 8801 " read "0.8801." 922. Table II., furnace C, item 2, under gas. For " 0.011 C " read " 0.011 0." Furnace G, item 13, under gas. For " 5.074 air " read " 3.074 air." Item 15, 114.269 " should be " 4.289." Furnace H, item 2, under iron. For " 0.04 " read ".0.01." 923. Table II., furnace J, item 1, under iron. For " 0.95 " read " 0.93." Furnace N2, item 6, under gas. For " 0.66 CO," read 0.066 C02." 924. Table III., furnace C, item 17. For " 379 " read " 397." 927. Table IV., furnace C, item 4. For " 0.0124 " read 0.0424." Furnace G, item 15.. For " 4,060 " read " 4,066." 928. Line 2. Items 19 and 20 of heat-supply, should be items 20 and 21. 930. Line 3. Expunge remainder of paragraph after the word " supplied," and substitute the following : "As compared with the fusion-zone, the loss by radiation n C was 25.5 per cent. of the total (2,278 units) supplied to that zone, while in D it was 22.5 per cent. of the total heat (1,824 units) supplied to that zone. Finally, as compared with the reduction-zone, C lost by radiation 36.8. per cent. of the 1,580 units supplied to that zone,

May 1, 1910

By G. Derge, W. Peifer, J. H. Richards

INTRODUCTION A WIDE variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware. They have been related to hydrogen largely by circumstantial evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British Committee on the Heterogeneity of Steel Ingots,1 and current approaches to the problem were reviewed in a recent symposium of the AIME.12 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principle object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem. The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow cooling. However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross section large enough to develop cracks, yet small enough for convenient handling and sampling. Rails were also selected because they are made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitates early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion. (2) Vacuum extraction (without melting). (3) Total combustion.

Jan 1, 1948

By E. T. Turkdogan, L. S. Darken, R. J. Fruehan

Further consideration is given to the application of the quadratic formalism to evaluate the thermodynamics of binary metallic solutions from experimental data. The use of the thermodynamic relation, in(r1/r2) dN2= 0, in the evaluation of activity data is discussed. The empirical correlations derived previously for enthalpies and entropies of solutions in Part II are shown to be predicted theoretically for a special case. The applicability of the quadratic formalism to the activity coefficients for binary organic solutions is demonstrated. DARKEN&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. In a subsequent paper (Part II) Turkdogan and Darkeen2 extended this formalism to the enthalpy and excess entropy of binary metallic solutions, and showed that the available data for the activity coefficients and heats of mixing of many solid and liquid binary metallic solutions confirm reasonable applicability of the quadratic formalism. Much variation was noted, however, in the extent of the terminal regions from one system to another, commonly from about 10 to 70 at. pct. For the present purpose, equations derived previously need be given only for one of the terminal regions, e.g. region (I), 0 < N2 < N&apos;2: where subscripts 1 and 2 indicate quantities for components 1 and 2 and superscript ° the values at infinite dilution; other terms are: N = atom fraction, y = activity coefficient, = partial molar enthalpy of solution, ?HM = molar heat of solution, ?Sx = excess partial molar entropy, ?Sx = excess molar entropy. The heat and entropy like terms (constants) el, and S12 are defined in the following expression for the temperature dependence of a12, thus a12 £12 — s12 rnl 2.303RT 2.303 R l J Using this formalism, the thermodynamics of binary systems in the terminal regions may be described over a temperature range of experisental interest in terms of eight quantities: Lº1—Lº2, ?Sx1,?Sxº2 , £12 ,£21,fiai, S12, and S21. In the previous paper, these quantities were evaluated for many solid and liquid binary solutions, and two significant correlations were observed between these thermodynamic quantities pertaining to the terminal regions, thus [10] and [11] Combining Eqs. [9], [l0], and [ll] and rearranging gives a12 -a21 = 1.382R log rº2- 0.08(?S2xº- ?S1xº) [12] Since the second term involving entropies is small and Eqs. 1101 and [ll] are empirical relations, the above equation may be simplified to a12 = 2.74 log rº2 [13] Using the values of a&apos;s and y°&apos;s compiled in Parts I and 11, a12 - a21 is plotted against log(rº2/rº1) in Fig. 1; the line drawn has a slope of 2.74. For Hg-K at 300°C, log(yº2 /yº1)= —5.10, not shown in Fig. 1, and from correlation [13], a12 - a21 = -13.97; this is to be compared with -10.76 derived from the activity data (Part II).

Jan 1, 1970

By John Chipman, Carl F. Floe

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry&apos;s law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts&apos; law. It may be recognized as a special case of Henry&apos;s law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By Carl F. Floe, John Chipman

The system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or CO2 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modern metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100" to 1500ºC., and pressures from about 20 mm. of mercury to somewhat above atmospheric. Review of Previous Work The solubility of gases in most liquids has been found to obey Henry&apos;s law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as O2, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts&apos; law. It may be recognized as a special case of Henry&apos;s law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: 2M+G2=2MG K=(MG)2 /M2 X PG2 [I] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: MG = K1 vPG2 [2 Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: 6Cu + SO2 = Cu2S + 2Cu2O [3] K= Cu2S X (Cu2O)2 i - (Cu)6(Pso2) [4] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: K1 =V3SO2 /Pso2 or

Jan 1, 1941

By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 &apos;poises&apos; times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By R. Floyd Farris

A method is presented for determining minimum waiting-on-cement time, which takes into account the differences that exist between types and brands of cements and such individual well conditions as depth, temperature, and pressure. The basis for the method was determined by laboratory tests. Being a laboratory development, several steps were required to prove its merit. The first step consisted of laboratory tests designed to determine the minimum cement strength required in wells. Basis was found for setting a minimum value of 8 Ib. per sq. in. tensile strength. Next, it was shown by laboratory tests that the time to 8 Ib. per sq. in. tensile strength may be expressed as a function of consistometer stirring time to loo "poises," the approximate relation being "the time to 8 Ib. per sq. in. tensile strength equals the time to I00 &apos;poises&apos; times three." Next, it was shown that the time of maximum temperature development in cement slurries, due to heat of hydration, is also related to consistometer stirring time to loo poises, but only by a factor of approximately two. It was shown also that the shut-in casing pressure will build up after cement is placed and register a maximum pressure at approximately the same time the slurry down the hole attains maximum temperature. From this and the relationships listed above, the general rule was established that minimum waiting-on-cement time (time to 8 Ib. per sq. in.) after casing cement jobs in any well is equal to the time when the shut-in casing pressure reaches a maximum, as measured from the initial mixing of cement, times a factor of 1.5. Cement plugs drilled in the field at the time prescribed by this formula were found to drill "firm to hard," thus confirming the laboratory tests. These tests prove that many of the present regulations for waiting on cement require a longer time than is absolutely necessary. Use of the method herein proposed offers the possibility of a saving of $1200 per well. Introduction The length of time allowed for cement to set after casing is determined either by state-wide rules, field rules, or self-imposed rules written into drilling contracts. In general, the time is dictated by experience and common practice. However, owing to differences in opinion and in experience of the various groups involved, waiting-on-cement time often varies from one area to the next. For example, an operator in an area where no rules exist may drill out of surface pipe at 24 to 36 hr., while another operator in another area may wait 48 hr. or more to comply with state or field rules, although the depth of the well, hole size, type of cement, and other data are identical. An even greater difference in practices will be found by making similar comparisons with respect to oil-string cement jobs. Differences in waiting-on-cement times of 36 to 48 hr. are common. Further complicating the picture is the rather common practice of allowing more waiting time for cement to set at the greater depths than is allowed at the shallow depths. This practice has existed for years in spite of the common knowl-edge1,2,3 that the temperature of the earth at the usual setting depths of surface

Jan 1, 1946

By J. B. Cheatham

The influence of friction on the force required for an idealized bit tooth to penetrate a "plastic" rock is analyzed. The rock is assumed to obey the Coulomb-Mobr yield criterion and the tooth is represented by a two-dimensional sharp wedge. At the tooth-rock interface the stress field not only satisfies the yield condition but also is such that the ratio of the shearing stress to the normal stress is equal to the coefficient of friction. The solution relates the force on the tooth to the depth of penetration, the tooth angle, the coefficient of friction between the rock and bit tooth and the angle of internal friction and compressive strength of the rock. INTRODUCTION Most rocks are brittle at atmospheric pressure but exhibit ductility and increased strength as the confining pressure is increased. In a previous analysisl the force required for a bit tooth to penetrate a rigid-plastic rock was computed for two limiting conditions: (1) a perfectly lubricated tooth-rock interface which should correspond to a lower limit for the penetrating force, and (2) a perfectly rough interface which should provide an upper limit. Experimental results2 for rock indentation under confining pressure have confirmed that the analysis generally predicts upper and lower limits for the penetrating force as a function of rock properties and tooth angle. The present analysis extends the previous work to account for the friction between the rock and the tooth. ANALYSIS The force required for incipient plastic flow of an idealized model of a rock under a bit tooth is computed subjected to the following assumptions. BIT TOOTH 1. sharp two-dimensional wedge (end effects neglected) 2. rigid tooth (elastic deformation of tooth neglected) 3. displacement of tooth is normal to rock surface 4. friction exists between tooth and rock ROCK 1. semi-infinite, isotropic and homogeneous 2. rigid-plastic (elastic deformation of rock neglected) 3. non-work hardening (horizontal stress-strain curve) 4. Coulomb yield condition* (linear Mohr envelope) 5. smooth, flat surface According to the Mohr theory of failure it is assumed that failure occurs when the state of stress is such that the Mohr stress circle becomes tangent to an experimentally determined envelope. The Mohr failure curve is frequent1y approximated by a straight line and referred to as the Coulomb-Mohr failure criterion. If the rock is under sufficient pressure to be ductile we can use the linear envelope as a yield condition. The Coulomb-Mohr yield criterion is illustrated by Fig. 1 and is expressed by the following equation:l

By E. F. Kingsbury

ONE of the well-known and important uses of the noble or precious metals has been for electrical contacts. In fact, the elements of this group, comprising gold, silver and. the six platinum metals, have been called "noble" because of their ability to resist heat and corrosion, properties which. were early found to be of importance in good contacts. Of these, platinum and its iridium alloys, palladium, and silver, have been extensively used. In recent years the electrical industry has been responsible for about one-eighth of the total consumption of the platinum metals in the United States. Information is not available as to what part of this one-eighth has been used for contacts but it is certainly an important one. SUBSTITUTES FOR PLATINUM During the past 20 years a considerable number of contact alloys have been proposed in the patent literature largely with the aim of more or less replacing platinum by gold or silver, and some of these alloys are finding increasingly widespread application as the reliability of their performance becomes established. From even the partial data at hand it appears that this substitution by the less precious metals has replaced at least one-half of the amount of platinum that the entire electrical industry would otherwise be consuming at the present time. While the subject is of considerable interest to the metallurgist it is even more so to the electrical engineer and it is surprising that the literature records no systematic and&apos; comprehensive investigation along these lines. Practically all the scattered work on noble metal contacts has centered around platinum as a standard and has had two more or less distinct aims. One of these has been the replacement of platinum by cheaper materials, and the other, the development of materials of superior electrical performance. The merit, of a contact metal has been assumed to be dependent on its infusibility, and since the more precious metals have the higher melting points there has naturally been an association of the two qualities in the sense that the more precious were

Jan 1, 1928