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By W. C. Merrill, P. G. Nahin, A. Grenall, R. S. Crog

A progress report of an experimental investigation into the role of clay in reservoir performance is presented. The Paper gives some of the reasons for considering clay as a significant component and outlines the objectives of a broad field of stud) which it is intended to pursue. Descriptions of the analytical methods used are given; these include X-ray diffraction. elec tron miscroscopy, thin section petrography, infrared spec-troscopy, and cation exchange analysis. A suite of the more important clay minerals has been assembled and characterized l~y these methods for use as standards in core analysis. From the data obtained it appears that although no one method of analysis is diagnostic for all of the clay minerals the infrared technique shows considerable promise in this direction. For the present, one or more supplementary methods should be used to confirm the clay mineral identifications. The methods of analysis are applied to field cores taken from repesentative and widely differing strata especially as regards their susceptibility to damage by fresh water. well.; completed in the stevens and Gatchell zones in San Joaquin valley are I,articularly clear-cut examples of this behavior with stevens zone wells being more adversely affected by fresh water. cores from these zones have been studied and are discussed. It appears that differences in this behavior can be ascribed to differences in the nature of the contained clays. The value of the infrarecl spectra of the clay fractions in establishing the identity of the predominant clay minerals is given particular emphasis. INTRODUCTION It is a challenge to the technical resources of the petroleum industry that when the economic limit of production is reached, from 40 to 70 per cent of the oil in California reservoirs remains unproduced even by use of the best presently known methods of recovery. The magnitude of this abandoned volume of oil can be appreciated when it is considered that to 1950 in excess of 8 billion bbll has been produced from California reservoirs with estimated economically recoverable reserves in known fields and pools totaling nearly 4 billion bbl.24 If for every barrel of oil produced there is at least another barrel still in place, it is evident that the revenue obtained from the recovery of only a .few per cent of this volume would repay the cost of the required research manyfold. From well completion experience. production behavior, and a growing body of laboratory data it now appears certain that the mineral composition of a producing stratum has an important bearing on the productivity and ultimate yield. In addition to the organic component and water, the cores con,ist of gravel, sand. silt, and clay" in diverse variety of (a, composition and (b) texture. It is the composite effect of these two factors which is probably responsible in large measure for the way in which the oil flows to the well. The role of the clay and fine-size accessory minerals is not clear but there is a growing opinion, based on their physical and chemical properties, that it is a significant one. of particular importance are the prime facts: 1. The silt and clay fractions of the reservoir matrix possess the highest surface area per gram, and 2. The silt and especially the clay fractions are the most chemically reactive of the inorganic constituents present. Only within the last few years has the knowledge of clay mineralogy and the techniques of identifying the clay minerals reached such a stage as to enable reliable inquiry into the composition of argillaceous sediments.2,8,10,11,12,16,26 It is the purpox of this and succeeding papers to add to the fund of information on the role which these materials play in the production of petroleum from California formations by correlating their presence and associated properties with observed reservoir behavior. In the present paper attention is directed to their possible influence on damage by fresh water. OBJECTIVES The attack on this problem divides naturally into two broad phases: 1. Determination of the nature of the clays and their relationships to the other mineral components, and 2. Determination of the physico-chemical relationships between the clays and the interstitial fluids. In the work described in this paper the emphasis has been on phase 1, which stems logically from the necessity of identifying and understanding the materials to be dealt with in Phase 2. Based on the authors' present opinion that not all of the minerals which occur in oil-bearing formation are of equal importance in their effects on the flow and recovery of oil, it was decided to focus attention first upon the clay minerals content and then. later perhaps. work into the field of the normally larger size non-clay minerals and fractions. The

Jan 1, 1951

By Herman Dykstra, R. L. Parsons

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By R. L. Parsons, Herman Dykstra

A numerical method for solving partial differential equations in steady state fluid flow is described. This method, known as the "relaxation method," has two advantages over analytical methods: (1) practically any problem can be solved, and (2) a solution can be obtained quickly. A disadvautage is that the solution is not general. The method is applied to core analysis and relative permeability measurement to calculate constriction effects and to calculate the true pressure drop measured by a center tap in a Hassler type relative permeability apparatus. Further applications are suggested. INTRODUCTION Many problems in fluid flow cannot be solved analytically because of the nature of the boundary conditions. For many problems, however. an exact answer is not necessary because boundary conditions are not exactly defined or the parameters describing the porous medium are not accurately known. The relaxation method can be used to obtain an approximate answer easily and quickly for the flow of incompressible fluids in porous media. The method can also be used for other types of problems, such as determining the stress in a shaft under load. or the temperature distribution during steady state heat flow. In this discussion only calculations concerned with the flow of fluids in porous media will be considered. The method was introduced by R. V. Southwell in 1935.' THEORY The treatment given here follows that given by Enimons.2 Consider a porous medium to be replaced entirely by a net of tubes of equal length and uniform cross-sectional area as shown in part in Fig. 1. Assume that the net of tubes behaves exactly like the porous medium which it replaces; that is, the net can be made fine enough to reproduce exactly the porous medium. Assume also that Darcy's Law can be used to calculate the flow from one point to another point through these tubes. The flow from point 1 to point 0 is KA . ------ P-P) .......(11 where a is the distance between points: K is the "permeability" of a tube; A is the cross-sectional area of a tube; is the viscosity of the liquid in the porous medium; and (P1 — P0) is the pressure difference between point 1 and point 0. In like manner the flow can be calculated from points 2, 3, and 4 to point 0. The net flow into point 0 is Qo = KA/µa (P1 + P2 + P33 + P4-4P0) . . (2) MB For an incompressible fluid the net flow into point 0 will be zero or, Q. = 0. This says that at point 0 fluid is neither being accumulated nor depleted. 'Therefore. P1 + P2 + P3 + P4 - 4P0 = 0 .... (3) . If. now. with specified boundary conditions. the pressure i.; known at a finite number of points in a given region, as at the points shown in Fig. 1, Equation (3) will be satisfied at every point. If, on the other hand, the pressure is not known, the pressure can be guessed at these points. Then. unless the guess is perfect. Equation (3) will not be satisfied at all of the points. When Equatiol~ (3,) is not satisfietl. let d = P1 + I?, + P, + P, - If' .,....(4) where 6 is an apparent error and is called the residual at point 0. Equation (4) shows how much the pressure guess is in error at point 0 with respect to the surrounding points. A positive residual means that the pressure is too low, and a negative residual means that the pressure is too high. To bring the residual, 6. to zero in order to satisfy Equation (3). it is necessary to make changes in the pressure guesses. Equation (4) shows that a +1 change in Po will change the residual at point 0 by -4. A +1 change in the pressure at any of the four surrounding points will change the residual at point 0 by +l. Thus it can be seen that a change at any point will affect the residual at that point and the four surrounding points. By changing the pressure from point to point, all of the residuals can eventually be brought nearly to zero and the problem will be solved. This procedure is the essence of relaxation methods and is used to relax the residuals so that Equation (3) is satisfied at every point. The procedure can be most easily explained in detail by solving a simple problem. as Southwell says, "To explain every detail of a practical technique is to risk an appearance of complexity and difficulty which may repel the reader. A

Jan 1, 1951

By J. E. Harris

The metallic elements, beryllium, calcium, cerium, lithium, manganese, titanium, vanadium and zirconium are used in metallurgical practice in relatively small percentages for the purpose of improving the physical properties of various alloys. No important uses for any of these elements have thus far been developed either in the pure form or in alloys of which they constitute the major constituent.

Jan 1, 1935

The Board of Directors has authorized the following offers of sets of back volumes of the Transactions, at considerably reduced prices, to Members, Libraries, and Scientific Societies Per Set. I. Five volumes, bound in half-morocco, from No. 36 (1906) to No. 40 (1910), . $20 II. Ten volumes, bound in half-morocco, from No. 31 (1902) to No. 40 (1910), including Mexican Volume, 35 III. Twenty volumes, bound in half-morocco, from No. 21 (1893) to No. 40 (1910), 50

Jan 4, 1913

C. R. CORNING, Chairman. ADOLPHE E. BORIE, First- Vice-Chairman. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. Vice-Chairmen. JOHN H. ALLEN, GEORGE M. COLVOCORESSES, RICHARD M. ATWATER, JR., -ROBERT PEELE, GEORGE D. BARRON, CHARLES P. PERIN, A. CHESTER BEATTY, JOSEPH A. VAN MATER, J. PARKE CHANNING, ARTHUR L. WALKER. D. C. Bard, Howard Eckfeldt, Milton H. McLean, W. de L. Benedict, R. C.Gemmell, ' Philip N. Moore, John C. Branner, F. Louis Grammer, T. H. O'Brien, Palmer Carter, Ernest A. Hersam, James J. Ormsbee, Allan J. Clark, Edwin C. Holden, Edward W. Parker, F. Crabtree, William L. Honnold, John B. Porter, George G. Crawford, Reginald E.. Hore, R. M. Raymond, O. C. Davidson, C. Colcock Jones; Robert B. Richard's, E. V. D'Invilliers, Eugene P. Kennedy, LeRoy Salsich, James S. Douglas, Chester F. Lee, Henry L. Smyth, Walter Douglas, Richard S. McCaffery, F. W. Traphagen, Howard N. Eavenson, James F. McClelland, Elton W. Walker. Meetings of this committee were held at the Institute headquarters on April 18, May, 3 and 15, and June 19.. At the meeting of June 19, the Secretary reported that letters of invitation to apply for membership in the Institute had been sent to all the alumni of the School of Mines of Columbia University and also to all State Mine Inspectors and their deputies. He also reported the securing of lists of the alumni of the Harvard Engineering Schools, and of the Mining Schools at Houghton, Mich. ; Butte, Mont. ; State College, Pa. ; Seattle, Wash. ; Fayetteville, Ark.; Laramie, Wyo.; Montreal, Canada, and Wor-cester and Rensselaer Polytechnic Institutes. Arrangements were made to invite all these to join the Institute. It was suggested that a. member' of the Institute resident in Australia be appointed to this Committee, also one from Japan. Attention of the members of the Committee was drawn to the fact that letters requesting, others to join the Institute will be written in the offices of the Institute if desired. The applications for membership received recently have been as follows March, 30; April, 02; May, 70; June, 54. The next meeting will be held July 17. THOMAS T. READ, Secretary.

Jan 7, 1913

INTERNATIONAL GEOLOGICAL CONGRESS. (For further particulars apply to the Secretary, 12th International Geological Congress, Victoria Memorial Museum, Ottawa, Canada ; cable address, Geocong, Ottawa.) The Coal Resources of the World.-Three quarto volumes of about 400 pages each, 8 1/4 by 10 3/4 in., and an atlas of about 70 maps in colors, 13 1/3 by 19 1/2 in., bound in heavy paper cover. Edition limited to 3,000 copies, One thousand copies will be reserved for members of the International Geological Congress, and the remainder of the edition will be distributed in the order in which applications are received. Price, $35 per set. Ready in July, 1913. This book is an inquiry made upon the initiative of the Executive Committee of the Twelfth International Geological Congress, with the assistance of geological surveys and mining geologists of different countries, published by: Morang & Co., Ltd., Toronto, Canada. Headquarters During Session at Toronto. The headquarters will be a t the University of Toronto, where there will be a branch post-office open at all hours and at which registered mail may be received or despatched, money orders sent or cashed, etc. A hank will be established at which money may be exchanged. A typewriting service will be maintained, also a telephone service and messenger service. Railway and steamship agents will also be in attendance. A restaurant service providing luncheon in the middle of the day will be arranged.

Jan 8, 1913

S. F. EMMONS RESEARCH FELLOWSHIP. The movement was started by a number of the friends and admirers of the late S. F. Emmons, Economic Geologist of the United States Geological Survey, to perpetuate his name through a fellowship to be known as the " S. F. Emmons Research Fellowship," and they have succeeded in raising some $13,000 for the purpose of carrying on research work in economic geology. The Committee in charge of this Memorial Fund has succeeded in obtaining the co-operation of Professors Kemp, of Columbia, Irving, of Yale, and Lindgren, of Massachusetts Institute of Technology, in the administration of this fellowship. These three gentlemen are respectively geologists of the institutions mentioned and are exceptionally qualified to determine in what direction the fund can be best administered. It is hoped that additional contributions will be forthcoming from many who have heard of this movement. Subscriptions are invited and may be sent to any one of these gentlemen, or to Benjamin B. Lawrence, Treasurer, No. 60 Wall Street, New York City.

Jan 11, 1913

COMMITTEE ON INCREASE OF. MEMBERSHIP. C. R. CORNING, Chairman. ADOLPHE E. BORIS, First Vice-Chairman. THOMAS T. READ, .Secretary, Woolworth Bldg., New York, N. Y. Vice-Chairmen. JOHN H. ALLEN, GEORGE M. COLVOCORESSES, RICHARD AL ATWATER, JR., ROBERT PEELS, GEORGE D. BARRON, CHARLES P. PERIN, A. CHESTER BEATTY, JOSEPH A. VAN MATER, J. PARKE CHANNING, ARTHUR L. WALKER. D. C. Bard, Howard Eckfeldt, Philip N, Moore, W. de L. Benedict, R. C. Gemmell, T. H. O'Brien, John C. Branner, F. Louis Grammer, James J. Ormsbee, Palmer Carter, Ernest A. Hersam, Edward W. Parker, Allen J. Clark, Edwin C. Holden, John B. Porter, F. Crabtree, William L. Honnold, R. M. Raymond, George G. Crawford, Reginald E. Hore, Robert H. Richards, O. C. Davidson, C. Colcock Jones, LeRoy Salsich, E. V. D' Invilliers, Eugene P. Kennedy, Frederick H. Sexton, James S. Douglas, Chester F. Lee, Henry L. Smyth, Walter Douglas, - Richard S. McCaffery, F. W. Traphagen, Howard N. Eavenson, James F. McClelland, Elton W. Walker. Milton H. McLean, Meetings of this committee were held at the Institute headquarters on April 18, and May 2 and 15. It was resolved that meetings shall be held monthly on the third Friday of each month.

Jan 6, 1913

S. F. EMMONS RESEARCH FELLOWSHIP. The movement was started by a number of the friends and admirers of the late S. F. Emmons, Economic Geologist of the United States Geological Survey, to perpetuate his name through a fellowship to be known as the ?S. F. Emmons Research Fellowship," and they have succeeded in raising some $13,000 for the purpose of carrying on research work in economic geology. The Committee in charge of this Memorial Fund has succeeded in obtaining the co-operation of Professors Kemp, of Columbia, Irving, of Yale, and Lindgren, of Massachusetts Institute of Technology, in the administration of this fellowship. These three gentlemen are respectively geologists of the institutions mentioned and are exceptionally qualified to determine in what direction the fund can be best administered. It is hoped that additional contributions will be forthcoming from many who have heard of this movement. Subscriptions are invited and may be sent to any one of these gentlemen, or to Benjamin B. Lawrence, Treasurer, No. 60 Wall Street, New York City.

Jan 10, 1913

Meetings of this committee were held at the Institute headquarters on April 18, May 2 and 15, and June 19. At the meeting of June 19, the Secretary reported that letters of invitation to apply for membership in the Institute had been sent to all the alumni of the School of Mines of Columbia University and also to all State Mine Inspectors and their deputies. He also reported the securing of lists of the alumni of the Harvard Engineering Schools, and of the Mining Schools at Houghton, Mich. ; Butte, Mont. ; State College, Pa.. ; Seattle, Wash.; Fayetteville, Ark. Laramie, Wyo.; Montreal, Canada, and Worcester and Rensselaer Polytechnic Institutes. Arrangements were made to invite all these to join the Institute. It. was suggested that a member of the Institute resident in Australia be appointed to this Committee, also one from Japan. Attention of the members of the Committee was drawn to the fact that letters requesting others to join the Institute will be written in the offices of the Institute if desired. The applications for membership received recently have been as follows: March, 30; April, 62; May, 70; June, 54. The next meeting will be held July 17. THOMAS T. READ, Secretary.

Jan 7, 1913

INTERNATIONAL ENGINEERING CONGRESS, 1915.. Announcement. In connection with the Panama-Pacific International Exposition which will be held in San Francisco in 1915, there will be an International Engineering Congress, in which engineers throughout the world will he invited to participate. The Congress is to be conducted under the auspices of the following five National Engineering Societies: American Society of Civil Engineers, American Institute of Mining Engineers, The American Society of Mechanical Engineers, American Institute of Electrical Engineers, and The Society of Naval Architects and Marine Engineers. These societies, acting in co-operation, have appointed a permanent Committee of Management, consisting of the Presidents and Secretaries of each of these Societies, and eighteen members resident, in San Francisco. Thus constituted, the personnel of the Committee 'is as follows:

Jan 9, 1913

By E. A. Gulbransen, J. W. Hickman

Recent work by the authors1 on the oxide films formed on alloys of titanium and zirconium with nickel and copper indicated that an investigation of the oxides which form on alloys of copper and nickel might permit the relative rates of formation and diffusion of the ions of these metals to be determined. This binary system is of further interest since the alloys which form are of the solid solution type over the entire range. In addition nickel is much more oxidation resistant than copper. A comparison of the free energies of formation of the simple oxides which may occur on these alloys indicates that nickel oxide should be observed over the entire time and temperature ranges of oxidation for all alloy compositions~i In order for nickel oxide to predominate on the surface, it is necessary that nickel ions form and diffuse to the surface. Two factors which may influence the formation of nickel oxide may be the ionic sizes, where cu+ is o.,,6-,4 and ~i++ is o.,oh;, and the charges on the ions. On the basis of size, Ni++ should diffuse more readily than Cu+ while on the basis of charge, Cu+ should form more readily than Ni++. According to Uhlig2 passivity to corrosion in an alloy appears at a critical composition which for copper-nickel alloys is related to the tendency of the d band of electronic energy states to fill with elec-trans. This in in the copper- nickel alloys corresponds to 40 at. pct nickel at which composition Uhlig2 (quoting La Que's data) states that the alloy system becomes passive. Magnetic and specific heat data indicate that the d band of copper-nickel alloys is flied at 60 at. Pet Or or 4O at. pct nickel. Matt and Jones3 have shown that if, on alloying nickel with copper, one considers a copper atom to be identical with a nickel atom except for an extra electron (nickel has the configuration: 3ds 4s2 and copper: 3 dl0 4s) then at 60 at. pct copper or 40 at. pct nickel enough electrons are contributed by copper to fill the d band of the alloy. At this composition the magnetic susceptibility approximates zero according to Grew.4 Although the electron diffraction data will not determine the rates of the several reactions which may occur during oxidation, yet a determination of the structures of the surface oxides may yield information concerning the relationships, if any, which may exist between the oxide structures which form and that composition where the magnetic susceptibility approximates zero. It is quite possible, of course, that the mechanisms of the oxidation and corrosion reactions may be so widely different that no correlations between them may be possible. Survey OF Literature The metals, copper and nickel, which are face-centered cubic, form solid solution alloys which are face-centered cubic with no superstructure for all compositions. Three oxides of nickel have been investigated structurally by X ray diffraction. Of

Jan 1, 1949

By E. A. Gulbransen, J. W. Hickman

DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may Occur to such a degree that oxides may form in the body Of the film and On the outer surface which are different from those that would normally form if the additional elements were not present. The use Of transmisson electron diffraction may aid us in jnterpreting these phenomena. UP to the Present time all Of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physica1 state of the "alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the remova1 of carbon by Oxygen in a decar-burization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with lifetime tests carried

Jan 1, 1949

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By C. O. Worden, E. K. Landgraf, C. A. Zapffe

Following the discovery of Parke and Ham that deoxidation control of cast molybdenum can be predicated upon simple fractographic examination, a special study of that metal was undertaken to investigate those patterns ascribed to forge-ability and nonforgeability. An elaborately developed system of cleavage patterns immediately rewarded the study; and they are reported here as a necessarily preliminary contribution calling attention to information which is both new in type and in origin. In general, the present observations confirm those of Parke and Ham, and Wood-side; but they also disclose a wealth of detail and correlated phenomena which greatly expand the earlier information. For example, the oxide pattern of nonforgeability is found to be complex, perhaps involving as many as three distinctive patterns, And the nature of the carbide seems to be at least twofold. In addition, transgranular facets are here shown for the first time. Elaborately complex, but in a characteristic manner, these facets depict distortion in original crystal growth which provides truly extraordinary patterns. No carbide and oxide forms display themselves transgranularly, except in profile as exceedingly thin superficial films at the grain boundaries. Crys-tallographic features are also rare—a condition undoubtedly resulting from the great substructural distortion; but occasionally registrations are found of cleavage on {00I}, and faulted areas believed to be Neumann-type deformation on I I121. Introduction Parbe and Ham,' and again Woodside,2 have reported that the forgeability of molybdenum cast by their Vacuum-electric-arc Process can be predicted with great dependability by a simple fractographic observation. They state that nonforgeability is the result of a grain boundary oxide which can be readily identified on the fracture facet at high magnification; and they convert the nonforgeable condition to a forgeable one by increasing the carbon content of the melt until the oxide structures subsequently observed in the fracto-graph become replaced by a second strongly marked pattern characteristic of carbide and coincidentally indicative of forgeability. Considerable importance immediately attaches to such observations: (I) because of their direct commercial application to one of metallurgy's inviting and relatively unexplored metals; (2) because of a general scientific curiosity regarding the nature of these characteristic markings; and (3) perhaps more important, because of

Jan 1, 1949

By E. V. Potter, E. T. Hayes, H. C. Lukens

Large volumes of hydrogen are liberated at the cathode during electrolytic precipitation of manganese. Most of the gas escapes from the electrolyte, but a considerable amount may be entrapped in the manganese plate. Gas has been observed to escape from manganese melts in puffs that bite at the surface. It has been reported that castings made with electrolytic manganese tend to rise in the molds; for this reason the manganese is often treated to remove hydrogen before the melt is made or it is premelted and used as cast manganese in making the alloys. The effect of hydrogen on the properties of manganese and its alloys is not known, but its effect on iron and iron alloys has been studied extensively.l.2 The close relationship between iron and manganese suggests that hydrogen may have a similar effect on the properties of manganese and its alloys. The purpose of this investigation was to determine the amount of hydrogen or other gases in typical commercial electrolytic manganese sheet and to investigate ways of removing it most conveniently. Apparatus The apparatus used is shown schematically in Fig. I. It consists of a chamber A in which the metal sample is placed, a vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The specimen chamber was made of two concentric quartz tubes. The outer one, a, connects with the closed gas system and is surrounded by the furnace G. A second tube, b, fits closely inside a and has a small end that projects into the space for the specimen and holds the thermocouple for measuring the temperature of the sample. The inner tube is joined to the outer tube outside the furnace, with rubber tape and sealing wax, to prevent gas leakage into or out of the closed system. This type of specimen container is loaded very easily and can be used several times if molten metal does not come in contact with the quartz. An ordinary mercury manometer B is used to measure the pressure in the system. The volume gauge C is essentially another mercury manometer, but the volume of the column is much larger than normal and the height of the mercury can be varied by raising or lowering the well H. In this apparatus the tube had a volume of IOO C.C. for a 60-cm. length. For larger changes in gas volumes, auxiliary containers F were used to increase the volume of the system by known amounts. Valves were arranged so that these auxiliary containers could be filled from the system and evacuated by the pump as often as necessary to accommodate the increases in the volume of gas in the system. The furnace G, used to heat the samples, was equipped with an automatic temperature controller, which maintained the desired temperatures within ± 5°C.

Jan 1, 1945

By J. W. Hickman

Most of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.' In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,~ nickel,= chromium,= copper,z tungsten,s molybdenum,3 beryllium,' uranium,' thorium,' titanium6 and zirconium6 while investigations are in progress on tantalum and columbium. The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally. Examples of solid solutions which may present difficulties are MOO* and WOp, Fe304 and FeO.CrnOa since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of loglo Kg for the several temperatures. AF"B = -RT In KR AF°R and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the the given in I 1 to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium oxide to form

Jan 1, 1949

By R. I. Jaffee, H. P. Nielsen

In recent years much attention has been given to high melting alloy systems. It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. Past Work Miillerl determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from I771 C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Miiller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and Jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at I000 C. Vines and WiseS report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. Materials The platinum powder used in this work was kindly supplied by the Research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio. It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HC1. The resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1949

By J. O. Mack, J. B. Russell

In recent years, solders containing 20 per cent tin with no bismuth or cadmium have been developed by a few companies, and personnel have been properly instructed in their use. In addition, since the tin shortage, a number of solders containing less than 10 per cent Sn, and some with no tin, are being used in special applications; however, a solder of this type has yet to be developed that is satisfactory for general use. Table i.—Composition Ranges Prescribed for a Commercial Substitute Solder Element Per Cent Tin............................ 18.0-20.0 Bismuth (maximum)a............ 0. 80 Silver.......................... O. 10-1. 25 Bismuth plus silver (minimum).... 0. 85 Antimony (maximum)............ o. 50 copper (maximum),,,,,,,,..,,,, 0. I3 Other elements, each (maximum)6 0.03 Lead........................... balance a When silver is present in excess of I per cent, the Bi content shall be 0.50 per cent or over. b Total not to exceed 0.10 per cent. The Purpose of this investigation was to develop an alloy containing a maximum of 15 per cent tin, with no cadmium or bismuth, having solder properties equivalent to or better than those of substitute solders now specified containing 18 to 20 per cent tin (Table I), or even approaching the properties of the standard 40 to 60 tin-lead solder. The wartime restriction of bismuth and cadmium, elements that have beneficial effects on fluidity, solidification range and strength, makes it increasingly difficult to develop a general-purpose solder containing a maximum of 15 per cent tin. In the course of this investigation, 11 elements were used in various combinations with the basic I5-85 tin-lead alloy. These elements were antimony, silver, copper, indium, thallium, lithium, calcium, barium, potassium, sodium and arsenic. In all, 116 low-tin solders were investigated, with the idea of developing a solder that will give satisfactory working properties, specifically in regard to "wetting" of copper, brass and iron, solidification range, capillarity and shear strength of a soldered joint. The relative importance of these various properties plays an important role in the search for substitute solders, since it is almost impossible to retain all of the desired qualities of a high-tin solder and still make drastic changes in the alloy composition. Because of the expected uses of a general-purpose solder, it is necessary that it have properties, especially in regard to wet-tability, that will enable it to be used on the metals in common use. Basic Considerations The maximum liquidus temperature of a solder is determined by the particular application involved and the temperature that can be obtained by the source of heat. If a soldering iron is used, it must not only

Jan 1, 1945